TWI406921B - Adhesive composition, adhesive sheet, and applications thereof - Google Patents

Description

Adhesive composition, adhesive sheet using the composition, and utilization thereof

The present invention relates to an adhesive composition for a flexible printed wiring board in which a semiconductor integrated circuit (IC) or the like is used, and a polyimide film or the like is used as a substrate film, and an adhesive sheet for a flexible printed wiring board. And various flexible printed wiring boards formed by using these, and the manufacturing methods of these.

In particular, it relates to an adhesive composition and an adhesive sheet for fixing a reinforcing material composed of metal, glass epoxy or polyimide, to a flexible printed wiring board; An adhesive composition for a conductive circuit side of a flexible printed wiring board; an adhesive composition and an adhesive sheet suitable for further laminating the flexible printed wiring boards; and further relates to the use of the adhesive composition Various flexible printed wiring boards which are laminated and have excellent adhesion and solder heat resistance.

A flexible printed wiring board having an increased amount of use in a printed wiring board type is provided with a conductive circuit in various methods on a substrate film.

As a method of providing a conductive circuit, for example, a photosensitive etching resist layer is formed on a copper foil of a flexible copper plate provided with a copper foil on a substrate film with or without an adhesive layer, and has a circuit pattern. The photomask film is exposed to light, and only the exposed portion is cured. Secondly, after removing the copper foil of the unexposed portion by etching, and then the remaining photoresist layer is peeled off, a conductive circuit can be formed from the copper foil. Alternatively, only necessary circuits may be provided on the substrate film by sputtering or plating.

In general, a flexible printed wiring board is used for those having conductivity on one surface, a conductive circuit on both surfaces, and a conductive circuit inside. Further, the base film is generally a plastic film having insulating properties and flexibility and heat resistance, such as a film of polyimide and polyethylene terephthalate (PET), and the copper foil is generally made of electrolytic copper foil or Rolled copper foil.

Here, various types of adhesives are used in the flexible printed wiring board.

For example, a copper foil for forming a conductive circuit is bonded to a base film to form an adhesive for a flexible copper plate, and a reinforcing material is attached to a conductive circuit portion where a flexible printed wiring board is not provided. An adhesive for attaching a cover film on the side of the conductive circuit on which the flexible printed wiring board is disposed; and further bonding a plurality of flexible printed wiring boards to each other to laminate a plurality of conductive layers Adhesives for the circuit layer.

In addition, in the present specification, the "portion where the conductive circuit is not provided" of the flexible printed wiring board is the surface on the reverse side of the surface on which the conductive circuit of the flexible printed wiring board is disposed, and means that the circuit is not provided at all. The surface also includes a portion where the circuit is not formed in the surface on the same side as the surface on which the conductive circuit of the flexible printed wiring board is disposed.

Further, the other use of the adhesive in the printed wiring board includes a package substrate necessary for manufacturing a semiconductor packaged ball grid array (BGA) excellent in light weight and low cost, and reinforcement. An adhesive to which a plate (a stiffener) or a heat release plate (heater) is adhered, and an adhesive to which an electromagnetic wave shielding material or the like is attached to a machine frame.

A flexible printed wiring board that increases the amount of use in a wiring board type is susceptible to physical damage due to weak strength. Therefore, a part of the wiring board is reinforced with a reinforcing material to improve mechanical strength and use. For example, the reinforcing material is adhered to a portion where the stress is concentrated in the terminal portion, the switch portion, or the like of the socket.

Further, in order to protect the conductive circuit on the flexible printed wiring board, prevent oxidation, and improve the flexibility of the conductive circuit, it is generally applied to the protective circuit surface and covered with an adhesive layer to protect and cover the plastic film. (This plastic film is also known as "cover film").

In addition, in order to increase the size and density of electronic devices, there is an increasing demand for multilayer printed wiring boards having a plurality of conductive circuit layers that can be effectively wired in a narrow space, and for bonding multiple flexible printed sheets. The wiring board and the printed wiring board in which a plurality of conductive circuit patterns are laminated have a high demand.

Many of the interlayer adhesive materials used in the conventional multilayer printed wiring board are thermosetting resin prepregs which are impregnated with a base material such as glass cloth by a thermosetting resin represented by an epoxy resin. However, in recent years, as the thickness of the multilayer printed wiring board is reduced and the density is increased, the interval between the plurality of laminated printed wiring boards is extremely narrow, so that the requirement of not using an interlayer adhesive material such as a glass cloth is high.

A plastic film which is a substrate of the flexible printed wiring board, a cover film for protecting a surface, or a package substrate of a BGA, and a polyimine film is often used, and heat resistance is good. Further, in the reinforcing material for a flexible printed wiring board, a reinforcing material for a BGA, a heat supplier, or an electromagnetic wave shielding material, a metal material such as a glass epoxy board or a stainless steel sheet (for example, a SUS board) or a poly A ruthenium imide film.

Therefore, the adhesive used for such applications and the adhesive for laminating the flexible printed wiring board are required to be made of a polyimide film, a glass epoxy board, and a polyimide film. The metal plate and the polyimide film adhere well to each other.

A reinforcing material and a cover film are attached to the flexible printed wiring board, or a plurality of flexible printed wiring boards are laminated to form a printed wiring board, and the same reinforcing material and a cover film are attached, and then electronic components are mounted on the wiring board.

In the method of mounting an electronic component on a wiring board, the entire wiring board including the solder portion formed by printing or coating is heated to about 230 to 280 ° C by infrared reflow or the like, and the electronic parts of the molten solder are bonded to the wiring board. Method (solder reflow). Further, a method of attaching a cover film to expose a part of the conductive circuit of the printed wiring board and bringing the exposed conductive circuit portion into contact with the molten solder is also employed.

Therefore, in the adhesive used for the above-mentioned various applications, heat resistance such as foaming or peeling does not occur through solder reflow, and it is required to have high heat resistance such as foaming or peeling even when contacted with molten solder. .

In addition, printed wiring boards are the base parts of the electronics field that are expanding in the market, and their manufacturing and processing points are scattered throughout the country. Therefore, it is desirable that the printed wiring board and the material for manufacturing it have a small change in characteristics and excellent storage stability even after transportation and storage processes under various conditions.

Now, for the adhesive used for the above-mentioned use for manufacturing a printed wiring board, for example, a mixture of an epoxy resin and an epoxy resin hardener is widely used as a hardening component, and in order to improve peel strength and impart flexibility, it is blended with propylene. An epoxy resin composition of a flexible component such as a nitrile butadiene rubber (for example, see Patent Document 1). Such an epoxy resin composition has high heat resistance and good substrate adhesion, but more than half of the composition is occupied by an epoxy resin and a hardener thereof, and the epoxy resin is semi-hardened (stage B). There are many cases of thinning. Therefore, it must be stored at a low temperature and has a problem of lack of storage stability.

In addition, an acrylic resin-based composition in which an epoxy resin is used as a matrix polymer and an epoxy resin is used as a curing component has been proposed (for example, refer to Patent Document 2 and Patent Document 3). Since the acrylic resin contains a functional group crosslinkable with the epoxy resin, and substantially no epoxy resin hardener is used, a composition having good storage stability and good adhesion to the metal material can be obtained. There is a problem that the adhesion of the polyimide film is insufficient.

In addition, it has been proposed to use a saturated polyester resin to reduce the amount of the hardening component, and to improve the storage stability, and to adjust the degree of hardening. However, there is a problem that the heat resistance of the solder is lowered (for example, refer to Patent Document 4 and Patent Document 5). .

In addition, an adhesive composition containing a urethane-based prepolymer composed of a diol and a diisocyanate and a diamine-based curing agent, which has an epoxy-based adhesive as a main component, has been proposed. Excellent copper foil/polyimine adhesion, good solder heat resistance. The adhesive composition is obtained by reacting a hardener diamine compound with an epoxy resin and a urethane prepolymer to obtain good heat resistance, but a functional group of the urethane prepolymer. The reactivity between the isocyanate group and the diamine-based curing agent is high, and it is difficult to achieve both storage stability and solder heat resistance (see Patent Document 6).

Further, an adhesive composition containing a resin having a urethane bond and/or a urea bond in a main chain and a thermosetting resin is also known (Patent Document 7). However, the resin having a urethane bond and/or a urea bond in the main chain disclosed in Patent Document 7 does not have a carboxyl group. Therefore, even if an epoxy resin is used as a thermosetting resin, no reaction occurs between the two resins, so that the solder has poor heat resistance. In particular, the solder heat resistance after humidification is remarkably lowered.

[Patent Document 1] Japanese Patent Laid-Open No. 4-370996

[Patent Document 2] Japanese Patent Laid-Open No. Hei 9-316398

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2002-12841

[Patent Document 4] Japanese Patent Laid-Open No. Hei 6-330014

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2000-273430

[Patent Document 6] Japanese Patent Laid-Open No. Hei 8-32230

[Patent Document 7] Japanese Patent Laid-Open No. Hei 10-178066

The present invention solves the problems of the adhesive composition for a conventional flexible printed wiring board and various constituent materials for a printed wiring board using the same, and aims to provide a polyimide film and conductivity. The adhesive composition of the circuit and the reinforcing material is excellent in adhesion and good in storage stability, and an adhesive composition having a hard layer having excellent solder heat resistance can be obtained, and various constituent materials for a printed wiring board obtained by using the adhesive can be provided.

The foregoing problems are solved according to the present invention by the adhesive composition (I) characterized by comprising a polyurethane polyurea resin (A) and an epoxy resin (B), the polyaminocarboxylic acid The ester polyurea resin (A) is an ethyl urethane prepolymer having an isocyanate group obtained by reacting a polyol compound (a), an organic diisocyanate (b) and a diol compound (c) having a carboxyl group (d) It is obtained by reacting the polyamine compound (e) and the monoamine compound (f) under the following conditions, and has a weight average molecular weight of 80,000 to 250,000 and an acid value of 3 to 25 mgKOH/g.

(i) The ratio of the isocyanate group of the ethyl carbamate prepolymer (d) having an isocyanate group to the amine group of the polyamino compound (e) and the monoamine compound (f) is an amine group/isocyanate group = 0.8 /1 to 0.999/1 (mole ratio); and (ii) a total of 100 mol% of the amine group of the polyamino compound (e) and the amine group of the monoamine compound (f), a polyamine compound ( The proportion of amine groups in e) is from 90.0 to 97.0 mol%.

Further, in a preferred aspect of the adhesive composition (I) of the present invention, the ethyl urethane prepolymer (d) having an isocyanate group is reacted under the following conditions: a polyol compound (a) The ratio of the hydroxyl group of the diol compound (c) having a carboxyl group to the isocyanate group of the organic diisocyanate (b) is in the range of isocyanate group / hydroxyl group = 1.05 / 1 to 1.50/1 (mole ratio).

Further, in a preferred aspect of the adhesive composition (I) of the present invention, the amine valence of the polyurethane polyurea resin (A) is from 0 to 1.5 mgKOH/g.

Further, in a preferred aspect of the adhesive composition (I) of the present invention, the number average molecular weight of the polyol compound (a) is from 1,000 to 5,000, and the weight of the ethyl urethane prepolymer (d) The average molecular weight is 10,000 to 50,000.

Further, in a preferred aspect of the adhesive composition (I) of the present invention, the epoxy resin (B) is contained in an amount of 5 to 100 parts by weight based on 100 parts by weight of the polyurethane polyurea resin (A). Share.

Further, in a preferred aspect of the adhesive composition (I) of the present invention, the filler (C) is contained, and in particular, it is filled with 100 parts by weight of the polyurethane polyurea resin (A). The agent (C) is 0.1 to 100 parts by weight.

Moreover, the present invention relates to an adhesive sheet having a curable adhesive layer (II) composed of the above-described adhesive composition (I) on a release sheet.

Further, in a preferred aspect of the adhesive sheet of the present invention, other peelable sheets are provided on the curable adhesive layer (II).

Moreover, the present invention relates to a reinforcing material having a pressure-sensitive adhesive layer for a flexible printed wiring board having a curable adhesive layer (II) formed of the above-described adhesive composition (I).

Moreover, the present invention relates to a flexible printed wiring board with a reinforcing material, which is characterized in that a portion of the flexible printed wiring board where no conductive circuit is provided is formed by the above-mentioned adhesive composition (I). The adhesive layer (III) is hardened to fix the reinforcing material.

Moreover, the present invention relates to a method of producing a flexible printed wiring board with a reinforcing material, characterized in that the reinforcing printed material is fixed to the flexible printed wiring board by using the above-mentioned adhesive sheet.

Moreover, the present invention relates to a method for producing a flexible printed wiring board with a reinforcing material, characterized in that the above-mentioned adhesive composition (I) is applied to a reinforcing material, and a curable adhesive layer (II) is provided. Next, the curable adhesive layer (II) is heated while being in contact with a portion of the flexible printed wiring board where no conductive circuit is provided, and is adhered and/or adhered to the contact.

Further, the present invention relates to the adhesion of the adhesive layer (II) of the curable adhesive layer (II) composed of the above-mentioned adhesive composition (I) between the plastic film and the protective film which have not been subjected to the release treatment. Plastic film.

Further, the present invention relates to a flexible printed wiring board with a cover film, characterized in that a surface of a conductive circuit side of a flexible printed wiring board having a conductive circuit on its surface is transmitted through the above-mentioned adhesive composition (I) The formed hardened adhesive layer (III) is coated with a plastic film which has not been subjected to peeling treatment.

Moreover, the present invention relates to a method of producing a flexible printed wiring board with a cover film, characterized in that the protective film of the adhesive film is peeled off from the plastic film with the adhesive layer, and the exposed curable adhesive layer (II) is The surface of the flexible printed wiring board having the conductive circuit on the surface of the conductive circuit is contacted and adhered, and/or heated after being adhered to the contact.

Moreover, the present invention relates to a method of producing a flexible printed wiring board with a cover film, characterized in that the above-mentioned adhesive composition (I) is applied to a surface of a plastic film which has not been subjected to peeling treatment to form a hardening. Adhesive layer (II), and secondly, the surface of the curable adhesive layer (II) on the side of the conductive circuit of the flexible printed wiring board having a conductive circuit on the surface and adhered thereto, and/or contacted After sticking, heat it while it is being applied.

Moreover, the present invention relates to a method of producing a flexible printed wiring board with a cover film, which is characterized in that the above-mentioned adhesive composition (I) is applied to a flexible printed wiring board having a conductive circuit on its surface. The surface on the side of the conductive circuit forms a hardenable adhesive layer (II), and secondly, the hardened adhesive layer (II) is contacted with the unpeeled plastic film and adhered, and/or adhered to the contact side. Heat up.

Further, the present invention relates to a printed wiring board formed by laminating a plurality of conductive circuit layers, which is characterized in that only one surface is passed through the hardened adhesive layer (III) formed of the above-mentioned adhesive composition (I). A surface on the side of the conductive circuit of the first single-sided printed wiring board (1) having a conductive circuit and a surface on the side of the conductive circuit of the second single-sided printed wiring board (1) having only one surface having a conductive circuit Or bonding one surface of the double-sided printed wiring board (2) having conductive circuits on both sides to the surface of the conductive circuit side of the single-sided printed wiring board (1) having only one surface having a conductive circuit; The surface of the first single-sided printed wiring board (1) having a conductive circuit on the conductive circuit side and the second single-sided printed wiring board (1) having a conductive circuit on only one surface are not provided with conductivity The surface of the circuit is bonded; or the surface of one of the two-sided printed wiring board (2) having the conductive circuit on both sides, and the surface of the single-sided printed wiring board (1) having the conductive circuit on only one surface, which is not provided with the conductive circuit Fit or have conductive circuits on both sides a surface of a two-sided printed wiring board (2), a surface of a second two-sided printed wiring board (2) having conductive circuits on both sides thereof; or a first one-sided printed wiring having a conductive circuit on only one surface The surface of the board (1) on which the conductive circuit is not provided is bonded to the surface of the second single-sided printed wiring board (1) having only one surface having a conductive circuit, and the conductive circuit is not provided.

Further, the present invention relates to a method of producing a printed wiring board formed by laminating a plurality of conductive circuit layers, characterized in that a peelable sheet is peeled off from the above-mentioned adhesive sheet, and the exposed curable adhesive layer (II) is exposed. Contacting the surface of the first single-sided printed wiring board (1) having a conductive circuit on the side of the conductive circuit, and secondly peeling off another peelable sheet, and contacting the exposed hardenable adhesive layer (II) Only the surface of the second single-sided printed wiring board (1) having a conductive circuit on the side of the conductive circuit is adhered, and/or heated after being adhered to the contact.

Further, the present invention relates to a method of producing a printed wiring board formed by laminating a plurality of conductive circuit layers, characterized in that a peelable sheet is peeled off from the above-mentioned adhesive sheet, and the exposed curable adhesive layer (II) is exposed. Contacting the surface of the first single-sided printed wiring board (1) having a conductive circuit on the side of the conductive circuit, and secondly peeling off another peelable sheet, and contacting the exposed hardenable adhesive layer (II) Only the surface of the second single-sided printed wiring board (1) having a conductive circuit on which the conductive circuit is not provided is adhered and/or adhered to the contact, and is heated; or peeled off by the adhesive sheet a peelable sheet which contacts the exposed curable adhesive layer (II) with a surface of the first single-sided printed wiring board (1) having only one surface having a conductive circuit and which is not provided with a conductive circuit, and secondly peels off another The peelable sheet adheres to the surface of the conductive circuit side of the second single-sided printed wiring board (1) having the conductive circuit on one surface and adheres to the exposed curable adhesive layer (II), and/or After the contact sticks, one While heating.

Further, the present invention relates to a method of producing a printed wiring board formed by laminating a plurality of conductive circuit layers, characterized in that a peelable sheet is peeled off from the above-mentioned adhesive sheet, and the exposed curable adhesive layer (II) is exposed. The surface of the single-sided printed wiring board (1) having only one surface having a conductive circuit is in contact with the surface on the side of the conductive circuit, and the other peelable sheet is peeled off, and the exposed hardened adhesive layer (II) has contact with both sides. The two sides of the conductive circuit are printed on one surface of the wiring board (2) and adhered, and/or heated after being contact-adhered; or a peelable sheet is peeled off from the adhesive sheet to expose the exposed hardenable adhesive. The agent layer (II) is in surface contact with one of the two-sided printed wiring board (2) having conductive circuits on both sides, and secondly peels off another peelable sheet, and the exposed hardened adhesive layer (II) is contacted with only one surface. The surface of the single-sided printed wiring board (1) having a conductive circuit on the side of the conductive circuit is adhered, and/or heated after being adhered to the contact.

Further, the present invention relates to a method of producing a printed wiring board formed by laminating a plurality of conductive circuit layers, characterized in that a peelable sheet is peeled off from the above-mentioned adhesive sheet, and the exposed curable adhesive layer (II) is exposed. The surface of the single-sided printed wiring board (1) having only one surface having a conductive circuit is not in contact with the surface on which the conductive circuit is provided, and the other peelable sheet is peeled off, and the exposed hardenable adhesive layer (II) is contacted on both sides. The surface of one of the two-sided printed wiring board (2) having a conductive circuit is adhered and/or heated after contact, or a peelable sheet is peeled off from the adhesive sheet to expose the cured layer. The adhesive layer (II) is in surface contact with one of the double-sided printed wiring boards (2) having conductive circuits on both sides, and secondly peels off another peelable sheet, and the exposed hardened adhesive layer (II) is contacted only one side. The surface of the single-sided printed wiring board (1) having a conductive circuit on the surface thereof is not provided with the surface of the conductive circuit, and is adhered, and/or heated after being adhered to the contact.

Further, the present invention relates to a method of producing a printed wiring board formed by laminating a plurality of conductive circuit layers, characterized in that a peelable sheet is peeled off from the above-mentioned adhesive sheet, and the exposed curable adhesive layer (II) is exposed. Contacting one surface of the first two-sided printed wiring board (2) having a conductive circuit on both sides, and secondly peeling off another peelable sheet, and exposing the exposed curable adhesive layer (II) to the two sides with a conductive circuit The surface of one of the two-sided printed wiring board (2) is adhered, and/or heated after being adhered to the contact.

Further, the present invention relates to a method of producing a printed wiring board formed by laminating a plurality of conductive circuit layers, characterized in that a peelable sheet is peeled off from the above-mentioned adhesive sheet, and the exposed curable adhesive layer (II) is exposed. Contact with a surface of the first single-sided printed wiring board (1) having only one conductive circuit and no conductive circuit, and secondly peeling off another peelable sheet, and contacting the exposed hardenable adhesive layer (II) Only the surface of the second single-sided printed wiring board (1) having a conductive circuit on the surface of the second single-sided printed wiring board (1) is not adhered to the surface, and is adhered, and/or heated after being adhered to the contact.

Further, the present invention relates to a method of manufacturing a printed wiring board formed by laminating a plurality of conductive circuit layers, characterized in that the above-mentioned adhesive composition (I) is applied to a first surface having a conductive circuit The surface of the single-sided printed wiring board (1) on the side of the conductive circuit forms a curable adhesive layer (II), and secondly, the first layer of the curable adhesive layer (II) has a conductive circuit while contacting only one surface. a surface of the second single-sided printed wiring board (1) on the side of the conductive circuit or a surface of the second single-sided printed wiring board (1) on which the conductive circuit is not provided and adhered, and/or after the contact is adhered, one side Heat up.

Further, the present invention relates to a method of producing a flexible printed wiring board formed by laminating a plurality of conductive circuit layers, characterized in that the above-mentioned adhesive composition (I) is applied to a surface having only a conductive circuit The surface of the single-sided printed wiring board (1) on the side of the conductive circuit forms a curable adhesive layer (II), and secondly, the curable adhesive layer (II) is printed on both sides with conductive circuits on both sides. a surface of one of the wiring boards (2) and adhered thereto, and/or heated after contact bonding; or the above-mentioned adhesive composition (I) is applied to both sides of the printed wiring board having conductive circuits on both sides (2) One surface forms a curable adhesive layer (II), and secondly, the curable adhesive layer (II) is electrically contacted with a single-sided printed wiring board (1) having a conductive circuit on only one surface. The surface on the side of the circuit is adhered and/or heated after being adhered to the contact.

Further, the present invention relates to a method of producing a printed wiring board formed by laminating a plurality of conductive circuit layers, characterized in that the above-mentioned adhesive composition (I) is applied to a double-sided printed wiring board having conductive circuits on both sides thereof. (2) One surface forms a hardenable adhesive layer (II), and secondly, the hardened adhesive layer (II) is contacted with a single-sided printed wiring board (1) having a conductive circuit on only one surface. The surface of the conductive circuit is placed and adhered, and/or heated after contact and adhesion.

Further, the present invention relates to a method of manufacturing a printed wiring board formed by laminating a plurality of conductive circuit layers, characterized in that the above-mentioned adhesive composition (I) is applied to a first two-sided printing having conductive circuits on both sides thereof. The surface of one of the wiring boards (2) forms a hardenable adhesive layer (II), and secondly, the hardened adhesive layer (II) is in contact with the second two-sided printed wiring board (2) having conductive circuits on both sides. One surface is adhered and/or heated after contact.

Further, the present invention relates to a method of manufacturing a printed wiring board formed by laminating a plurality of conductive circuit layers, characterized in that the above-mentioned adhesive composition (I) is applied to a first surface having a conductive circuit The surface of the single-sided printed wiring board (1) is not provided with a conductive circuit to form a curable adhesive layer (II), and secondly, the curable adhesive layer (II) is provided with a conductive circuit while contacting only one surface. a surface on the conductive circuit side of the single-sided printed wiring board (1) or a surface on which the conductive circuit is not provided on the second single-sided printed wiring board (1), and is adhered, and/or adhered after contact While heating.

Further, the present invention relates to a method of producing a printed wiring board formed by laminating a plurality of conductive circuit layers, characterized in that the above-mentioned adhesive composition (I) is applied to one side having a conductive circuit on only one surface The surface of the printed wiring board (1) is not provided with a conductive circuit to form a curable adhesive layer (II), and secondly, the curable adhesive layer (II) is in contact with both sides of the printed wiring board having conductive circuits on both sides ( 2) One of the surfaces is adhered and/or heated after being contacted and adhered.

Further, the present invention relates to a method of manufacturing a printed wiring board formed by laminating a plurality of conductive circuit layers, characterized in that a curable adhesive layer (II) of the adhesive sheet has a conductive circuit on only one surface. The first single-sided printed wiring board (1) is in contact with the surface on the side of the conductive circuit, and secondly, the peelable sheet is peeled off, and the exposed curable adhesive layer (II) is in contact with only one surface and has a conductive circuit. a surface of the second single-sided printed wiring board (1) on the side of the conductive circuit or a surface of the second single-sided printed wiring board (1) on which the conductive circuit is not provided and adhered, and/or after the contact is adhered, one side Heating; or, the hardenable adhesive layer (II) of the adhesive sheet is brought into contact with a surface of the first single-sided printed wiring board (1) having only one surface having a conductive circuit without a conductive circuit, and secondly The peelable sheet is peeled off, and the exposed curable adhesive layer (II) is brought into contact with the surface of the conductive circuit side of the second single-sided printed wiring board (1) having a conductive circuit on one surface and adhered thereto, and / After the contact sticks, go ahead Line heating.

Further, the present invention relates to a method of manufacturing a printed wiring board formed by laminating a plurality of conductive circuit layers, characterized in that a curable adhesive layer (II) of the adhesive sheet has a conductive circuit on only one surface. The surface of the single-sided printed wiring board (1) is in surface contact with the conductive circuit side, and then the peelable sheet is peeled off, and the exposed curable adhesive layer (II) is contacted with both sides of the printed wiring board having conductive circuits on both sides ( 2) one surface is adhered and/or heated after contact bonding; or the hardenable adhesive layer (II) of the adhesive sheet and the double-sided printed wiring board having conductive circuits on both sides (2) One of the surface contacts, and then the peelable sheet is peeled off, and the exposed curable adhesive layer (II) is contacted with the conductive circuit side of the single-sided printed wiring board (1) having only one surface and having a conductive circuit. The surface is tacky and/or heated after contact.

Further, the present invention relates to a method of manufacturing a printed wiring board formed by laminating a plurality of conductive circuit layers, characterized in that a curable adhesive layer (II) of the adhesive sheet has a conductive circuit on only one surface. The surface of the single-sided printed wiring board (1) is not provided with the surface of the conductive circuit, and the peelable sheet is peeled off, and the exposed curable adhesive layer (II) is contacted with both sides of the printed wiring board having the conductive circuits on both sides. (2) one surface is adhered and/or heated after contact bonding; or the hardenable adhesive layer (II) of the adhesive sheet and the printed wiring on both sides having a conductive circuit One of the plates (2) is in surface contact, and then the peelable sheet is peeled off, and the exposed hardenable adhesive layer (II) is not provided with conductive light on the single-sided printed wiring board (1) having a conductive circuit on only one surface. The surface of the circuit is adhered and/or heated after being adhered to the contact.

Further, the present invention relates to a method of manufacturing a printed wiring board in which a plurality of conductive circuit layers are laminated, characterized in that the curable adhesive layer (II) of the adhesive sheet and the first two sides having conductive circuits on both sides One of the printed wiring boards (2) is in surface contact, and secondly, the peelable sheet is peeled off, and the exposed hardenable adhesive layer (II) is contacted with one surface of the second two-sided printed wiring board (2) having conductive circuits on both sides. And it is sticky, and/or heated after contact and sticking.

Furthermore, the present invention relates to a method of producing a printed wiring board formed by laminating a plurality of conductive circuit layers, characterized in that the curable adhesive layer (II) of the adhesive sheet is electrically conductive to only one surface. The surface of the first single-sided printed wiring board (1) of the circuit is not provided with the surface of the conductive circuit, and then the peelable sheet is peeled off, and the exposed curable adhesive layer (II) has a conductive circuit while contacting only one surface. The second single-sided printed wiring board (1) is not provided with the surface of the conductive circuit and is adhered, and/or heated after contact bonding.

The adhesive composition of the present invention is excellent in adhesion strength to a polyimide film, a conductive circuit, and a reinforcing material, and has good storage stability, and can obtain a hardened layer having excellent solder heat resistance, so it is suitable for use in flexibility. The lamination of the printed wiring board or the adhesion of the cover film for protecting the reinforcing material and the conductive circuit. Further, since the adhesive composition and the curable adhesive layer formed therefrom are excellent in storage stability, the change in characteristics is small even after the transportation and storage processes under various conditions.

Further, the adhesive composition of the present invention can be stored at room temperature, using an adhesive sheet formed thereof, a reinforcing agent with an adhesive layer for a flexible printed wiring board, or a cover film with an adhesive layer. It is not necessary to store such as low temperature.

First, the adhesive composition (I) of the present invention will be explained.

The polyurethane polyurea resin (A) contained in the adhesive composition (I) is obtained by reacting a polyol compound (a), an organic diisocyanate (b), and a diol compound (c) having a carboxyl group. The ethyl urethane prepolymer (d) having an isocyanate group is obtained by reacting with the polyamino compound (e) and the monoamine compound (f).

In the present specification, the "polyol compound (a)" is a compound generally known as a polyol component constituting a usual polyurethane resin, and a carboxyl group-containing diol which is a component (c) described later is used. As the compound other than the compound, for example, various polyether polyols other than the diol compound containing a carboxyl group, polyester polyols, polycarbonate polyols, polybutadiene diols, or the like can be used. Mixture, etc.

Examples of the polyether polyols include polymers such as oxidized ethyl, oxidized propyl or tetrahydrofuran, and the like.

Examples of the polyester polyol include ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,3-butylene glycol, 1,4-butanediol, neopentyl glycol, and pentanediol. 3-methyl-1,5-pentanediol, hexanediol, octanediol, 1,4-butanediol, diethylene glycol, triethylene glycol, dipropylene glycol, or dimer diol Saturated or unsaturated low molecular weight glycols, with adipic acid, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, a polyester polyol obtained by reacting a dicarboxylic acid such as glutaric acid, pimelic acid, behenic acid, citric acid or citric acid or an anhydride thereof; or n-butylepoxypropyl ether or 2- Ethyl hexyl epoxypropyl ethers of ethylhexyl epoxypropyl ether, glycidyl carboxylic acid monocarboxylates such as glycidyl acrylate, and anhydrides of the above dicarboxylic acids in alcohols A polyester polyol obtained by reacting in the presence of a hydroxyl group-containing compound; or a polyester polyol obtained by ring-opening polymerization of a cyclic ester compound.

As the polycarbonate polyol, for example, 1) a reaction product of a diol or a bisphenol with a carbonate; or 2) a reaction product obtained by reacting a diol or a bisphenol with a phosgene in the presence of a base, or the like can be used.

Examples of the carbonate used in the case of the above 1) include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethyl carbonate or propylene carbonate.

The diol used in the case of the above 1) or 2) may, for example, be ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, butylene glycol, 3-methyl-1,5- Pentandiol, 2-methyl-1,8-octanediol, 3,3'-dimethylol heptane, polyoxyethylene glycol, polyoxypropylene glycol, propylene glycol, 1,3-butanediol, 1 , 4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, octanediol, butylethylpentanediol, 2- Ethyl-1,3-hexanediol, cyclohexanediol, 3,9-bis(1,1-dimethyl-2-hydroxyethyl, or 2,2,8,10-tetraoxaspiro[ 5.5] Undecane and the like.

Further, examples of the bisphenol used in the case of the above 1) or 2) include bisphenols such as bisphenol A and bisphenol F, or addition of ethylene oxide or epoxy to the bisphenols. A compound of an alkylene oxide such as propane.

Examples of the base used in the case of the above 2) include sodium hydroxide or potassium hydroxide.

The number average molecular weight (Mn) of the polyol compound (a) is appropriately determined in consideration of heat resistance, adhesion strength, solubility, and the like of the obtained polyurethane urethane resin (A), but it is usually 1,000 to 5,000. The range is preferably, and more preferably from 1000 to 4000. If the Mn is less than 1,000, the urethane bond in the polyurethane polyurea resin (A) becomes excessive, and the flexibility of the polymer skeleton is lowered, and the polyimide film and the conductive circuit are used. The adhesiveness tends to decrease. When Mn exceeds 5,000, the molecular weight between the crosslinking points increases, and the solder heat resistance tends to decrease.

The above polyol compound (a) may be used alone or in combination of two or more. Further, in the range where the adhesive property of the polyurethane polyurea resin (A) is not lost, a low molecular weight diol may be used instead of a part of the above polyol compound (a), for example, the aforementioned polyol compound is used. Various low molecular weight diols having a molecular weight of about 400 or less used in the production.

As the organic diisocyanate compound (b), for example, an aromatic diisocyanate, an aliphatic diisocyanate, an alicyclic isocyanate or the like can be used, and particularly, isophorone diisocyanate is preferred.

Examples of the aromatic diisocyanate include 1,5-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, and 4,4'-benzyl ester. Isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, toluene diisocyanate, or xylene Diisocyanate and the like.

Examples of the aliphatic diisocyanate include butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and quaternary acid diisocyanate.

Examples of the alicyclic diisocyanate include cyclohexane-1,4-diisocyanate and isophorone diisocyanate. Alkyl diisocyanatomethyl ester, bis(4-isocyanate cyclohexyl)methane, 1,3-bis(isocyanatomethyl)cyclohexane or methylcyclohexane diisocyanate.

Examples of the diol compound (c) having a carboxyl group include a dimethylol alkanoic acid such as dimethylolacetic acid, dimethylolpropionic acid, dimethylolbutanoic acid or dimethylolvaleric acid; Dihydroxysuccinic acid; or dihydroxybenzoic acid. In particular, dimethylolpropionic acid or dimethylolbutanoic acid is preferred from the viewpoint of reactivity or solubility.

The condition in which the polyol compound (a) and the organic diisocyanate (b) are reacted with the diol compound (c) having a carboxyl group to obtain an ethyl carbamate prepolymer (d) having an isocyanate group, preferably in a plurality of In terms of the total hydroxyl group of the alcohol compound (a) and the diol compound (c) having a carboxyl group and the isocyanate group of the organic diisocyanate (b), the ratio of the isocyanate group to the hydroxyl group is from 1.05/1 to 1.50/1 in terms of a molar ratio. The reaction is carried out within the range, more preferably from 1.10/1 to 1.45/1. When the molar ratio of the isocyanate group to the hydroxyl group is less than 1.05/1, the polyurethane bond of the polyurethane polyurea resin (A) is small, and the film formability is lowered. If it exceeds 1.50/1, it is not easy to obtain. A polyurethane urethane resin (A) having a weight average molecular weight necessary for exhibiting sufficient solder heat resistance.

Further, the ratio of the polyol compound (a) to the diol compound (c) having a carboxyl group is not particularly limited, but the molar ratio of the polyol compound (a) / the diol compound (c) having a carboxyl group is preferably The range of 95/5~20/80, more preferably the range of 90/10~35/65. When the molar ratio of the polyol compound (a) / the diol compound (c) having a carboxyl group exceeds 95/5, the crosslinking of the polyurethane urethane resin (A) and the epoxy resin (B) When it is too small, the heat resistance is lowered, and if it is less than 20/80, the crosslinking of the polyurethane polyurea resin (A) and the epoxy resin (B) becomes excessive, and the adhesiveness is lowered.

The above reaction is usually carried out at a temperature of from ordinary temperature to 150 ° C, and more preferably from 60 to 120 ° C in terms of production time or control of side reactions.

The weight average molecular weight of the obtained isocyanate group-containing ethyl urethane prepolymer (d) is preferably in the range of 10,000 to 50,000, and more preferably in the range of 12,000 to 40,000. When the Mw is less than 10,000, it is not easy to obtain a polyurethane urethane resin having a weight average molecular weight which is required for exhibiting sufficient solder heat resistance. When the Mw is more than 50,000, the viscosity of the adhesive composition is high. The operability is lowered, so it is not good.

The polyurethane polyurea resin (A) can be obtained by reacting an aminourethane prepolymer (d) having an isocyanate group with a polyamine compound (e) and a monoamine compound (f).

The polyamine compound (e) acts as a chain extender, for example, in addition to ethylenediamine, propylenediamine, hexamethylenediamine, diethylidenetriamine, triethylidenetetraamine, isophorone II Amine, dicyclohexylmethane-4,4'-diamine or lower In addition to the alkyldiamine, 2-(2-aminoethylamino)ethanol, 2-hydroxyethylethylenediamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine or two may also be used. An amine having a hydroxyl group such as 2-hydroxypropylethylenediamine. Among them, isophorone diamine is more suitable for use.

The monoamine compound (f) functions as a molecular weight modifier of the polyurethane polyurethane resin, and for example, a dialkylamine such as di-n-butylamine or a dialkanolamine such as diethanolamine, or Alcohols such as ethanol or isopropanol.

As a condition for reacting the ethyl carbamate prepolymer (d) having an isocyanate group with the polyamino compound (e) and the monoamine compound (f), the ethyl urethane prepolymer (d) In the case where the amount of the free isocyanate group is used as a standard, it is important that the total molar ratio of the amine groups of the polyamino compound (e) and the monoamine compound (f) is in the range of 0.8 to 0.999, preferably Range of 0.85~0.995. When the total molar ratio of the amine groups is less than 0.8, the molecular weight of the polyurethane polyurea resin cannot be sufficiently increased, so that the solder heat resistance is insufficient. When the total molar ratio is more than 0.999, the polyamine compound (e) and the monoamine compound (f) are easily unreacted and remain in a large amount, and directly react with the epoxy resin in the adhesive composition, or display a catalyst. The activity makes the preservation stability of the adhesive composition lower, which is not preferable.

Further, in the total of 100 mol% of the amine group of the polyamino compound (e) and the amine group of the monoamine compound (f), the amine group of the polyamino compound (e) is 90.0 mol% to 97.0 mol. % is important, preferably in the range of 92.0 mol% to 96.0 mol%. When the ratio of the amine group of the polyamine-based compound (e) is less than 90.0 mol%, it is difficult to obtain a polyurethane urethane resin having a weight average molecular weight necessary for exhibiting sufficient solder heat resistance. Further, when the proportion of the amine group of the polyamino compound (e) is more than 97.0 mol%, the viscosity of the adhesive composition is high, workability is lowered, and the amine compound is liable to react in a large amount, and is composed of an adhesive. The epoxy resin reacts directly or exhibits catalytic activity, which makes the storage stability of the adhesive composition lower, which is not preferable.

The weight average molecular weight (Mw) of the polyurethane polyurea resin (A) is in the range of 80,000 to 250,000, and is preferably in the range of 90,000 to 200,000. When the weight average molecular weight is less than 80000, the solder has poor heat resistance. When the weight average molecular weight is more than 250,000, the viscosity of the resin solution is high, and workability is lowered, which is not preferable.

Further, the acid value of the polyurethane polyurea resin (A) must be in the range of 3 to 25 mgKOH/g, preferably in the range of 7 to 20 mgKOH/g. Further, the acid value is based on the acid value of the carboxyl group and is a solid component with respect to the polyurethane polyurea resin (A). When the acid value of the polyurethane polyurea resin (A) is less than 3 mgKOH/g, the crosslinking with the epoxy resin contained in the adhesive composition (I) is insufficient, and the adhesive layer after hardening is obtained. The heat resistance is lowered, and the solder heat resistance cannot be expressed. Further, in the case where the acid value is more than 25 mgKOH/g, the epoxy resin contained in the adhesive composition (I) is excessively crosslinked, and is applied to a adherend (for example, a plastic film such as a polyimide film, a glass epoxy board, or the like). The peel strength of the metal plate or the like is lowered.

Further, the amine valence of the polyurethane polyurea resin (A) is preferably in the range of 0 to 1.5 mgKOH/g, more preferably in the range of 0 to 1.2 mgKOH/g. In addition, the amine valence here is the number of mg of potassium hydroxide and the potassium hydroxide necessary for neutralizing the solid content of 1 part of the polyurethane polyurea resin (A), and the polyaminocarboxylic acid. The amount of the unreacted polyamine compound (e) and the monoamine compound (f) contained in the ester polyurea resin is proportional. When the amine value is more than 1.5 mgKOH/g, the unreacted polyamine compound (e) and the monoamine compound (f) may directly react with the epoxy resin in the adhesive composition, or may exhibit catalytic activity to cause adhesion. The preservation stability of the composition of the agent is lowered, which is relatively poor.

The amine valence is determined by the following formula. That is, a solution of about 30 g of the polyurethane polyurea resin is dissolved in a mixed solution of methanol / n-butanol / toluene = 40 mL / 20 mL / 40 mL, and titrated with a 0.1 N aqueous solution of hydrochloric acid to obtain a neutralization solution. The amount of aqueous hydrochloric acid necessary. The number of milligrams of potassium hydroxide of the hydrochloric acid contained in the hydrochloric acid aqueous solution was converted into a solid content per 1 g of the polyurethane polyurea resin, and this was used as the amine value (mgKOH/g).

Further, when the polyurethane prepolymer (d) having an isocyanate group is reacted (ureaized) with the polyamine compound (e) and the monoamine compound (f), the reaction temperature can be appropriately adjusted to cause urea. Fully proceed. In general, the reaction temperature of the isocyanate group and the amine group from about room temperature to about 50 ° C is a quantitative reaction, but when a polyurethane urethane resin having a weight average molecular weight specified by the present invention is obtained, it is preferable to The higher reaction temperature allows the uread to proceed sufficiently. It is preferably 70 to 100 ° C, more preferably 75 ° C to 95 ° C. If the reaction temperature is less than 70 ° C, the urea formation reaction is difficult to complete, and the unreacted amine compound lowers the storage stability of the adhesive composition, which is not preferable. Moreover, when it exceeds 100 ° C, there is a possibility that an isocyanate group may react with a functional group other than an amine group, which is not preferable.

In the synthesis of the polyurethane polyurea resin (A), for example, an ester solvent, a ketone solvent, a glycol ether solvent, an aliphatic solvent, an aromatic solvent, an alcohol solvent, or the like can be used. A compound selected from a carbonate solvent or water, or the like, may be used alone or in combination of two or more kinds thereof as a solvent.

Examples of the ester solvent include ethyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, amyl acetate or ethyl lactate.

Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone benzene, diisobutyl ketone, diacetone alcohol, isophorone, and cyclohexanone.

Examples of the glycol ether solvent include ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, and propylene glycol monomethyl ether. Propylene glycol monoethyl ether or acetate of such monoethers; or diethers such as diethylene glycol dimethyl ether or diethylene glycol diethyl ether.

Examples of the aliphatic solvent include n-heptane, n-hexane, cyclohexane, methylcyclohexane, and ethylcyclohexane.

Examples of the aromatic solvent include toluene or xylene.

Examples of the alcohol solvent include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol or cyclohexanol.

Examples of the carbonate-based solvent include dimethyl carbonate, ethyl methyl carbonate or di-n-butyl carbonate.

Further, those having a hydroxyl group among the above various solvents cannot be used in obtaining the ethyl carbamate prepolymer (d) having an isocyanate group. However, when the aminourethane prepolymer (d) having an isocyanate group is reacted (ureaized) with the monoamine compound (e) and the monoamine compound (f), a solvent having a hydroxyl group can be suitably used. The reaction of the amine group with the isocyanate group is much faster than the reaction of the hydroxyl group with the isocyanate group. When a urea bond is formed by the reaction of a hydroxyl group and an isocyanate group, since a hydrogen bond is strong, the reaction solution is remarkably imminent and high viscosity. If a solvent having a hydroxyl group is used in the esterification of the urethane, the increase in the hydrogen bond can be alleviated.

Further, the epoxy resin (B) contained in the adhesive composition (I) of the present invention is a compound having an epoxy group, and may be liquid or solid, and is not particularly limited, but preferably one molecule is used. Among them, there are an average of two or more epoxy groups. As the epoxy resin (B), for example, a epoxidized propyl ether type epoxy resin, a epoxy propyl amine type epoxy resin, a glycidyl acrylate type epoxy resin or a cyclic aliphatic (alicyclic) epoxy resin can be used. Epoxy resin such as resin.

Examples of the epoxy propyl ether type epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, and cresol novolak type ring. Oxygen resin, phenol novolak type epoxy resin, α-naphthol novolac type epoxy resin, bisphenol A novolak type epoxy resin, dicyclopentadiene type epoxy resin, tetrabromobisphenol A type epoxy Resin, brominated phenol novolac type epoxy resin, tris(epoxypropyloxyphenyl)methane or tetrakis(epoxypropyloxyphenyl)ethane.

The epoxypropylamine type epoxy resin may, for example, be tetraglycidyldiaminediphenylmethane, triepoxypropyl-aminophenol, triepoxypropyl-aminophenol or tetra-epoxypropyl group. Meta-xylene diamine and the like.

Examples of the epoxy propyl ester type epoxy resin include diepoxy propyl phthalate, diepoxy hexahydrophthalate or dipoxypropyl tetrahydro phthalate.

Examples of the cyclic aliphatic (alicyclic) epoxy resin include epoxycyclohexylmethylepoxycyclohexanecarboxylate or bis(epoxycyclohexyl)adipate.

The epoxy resin (B) may be used alone or in combination of two or more.

Epoxy resin (B) is made of bisphenol A type epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin, and tris(epoxypropyl) from the viewpoint of high adhesion and heat resistance. Preferably, oxyphenyl)methane or tetrakis(epoxypropyloxyphenyl)ethane is preferred.

The adhesive composition (I) of the present invention preferably contains 5 to 100 parts by weight of the epoxy resin (B) based on 100 parts by weight of the polyurethane polyurea resin (A), and contains 7 to 90 parts by weight. For better. If the amount of the epoxy resin (B) is less than 5 parts by weight, it is difficult to express solder heat resistance. When the epoxy resin (B) is more than 100 parts by weight, the adhesion to a plastic film such as a polyimide film or a conductive circuit tends to be lowered.

In the adhesive composition (I) used in the present invention, the purpose of promoting the reaction of the polyurethane polyurea resin (A) with the epoxy resin (B) or the reaction of the epoxy resin (B) with each other is promoted. In the following, a hardening accelerator and/or a hardener may be contained. As the hardening accelerator of the epoxy resin (B), for example, a tertiary amine compound, a phosphine compound or an imidazole compound can be used, and as the curing agent, dicyandiamide, carboxylic acid hydrazine or an acid anhydride can be used.

The tertiary amine compound as a hardening accelerator may, for example, be triethylamine, benzyldimethylamine, 1,8-difluorenebicyclo (5.4.0) undecene-7 or 1,5-diguanidine (4.3). .0) Terpene-5 and the like. Further, examples of the phosphine compound include triphenylphosphine and tributylphosphine. Further, examples of the imidazole compound include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 2,4-dimethylimidazole or 2-phenylimidazole. . Further, a latent curing accelerator which improves the stability of storage, such as a type which reacts an imidazole compound with an epoxy resin and is insolubilized in a solvent, or a type in which an imidazole compound is encapsulated in a microcapsule, may be mentioned. A sexual hardening accelerator is preferred.

Examples of the carboxylic acid hydrazine as the curing agent include cesium succinate or cesium adipate. Further, examples of the acid anhydride include hexahydrophthalic anhydride or trimellitic anhydride.

These hardening accelerators or hardeners may be used alone or in combination of two or more of the foregoing compounds, and the content thereof is preferably from 0.1 to 30 parts by weight based on 100 parts by weight of the epoxy resin (B). .

The adhesive composition (I) of the present invention may contain a filler (C) for the purpose of improving the heat resistance of the solder, the heat transfer rate, or controlling the fluidity of the adhesive.

Examples of the filler (C) include cerium oxide, aluminum oxide, aluminum hydroxide, magnesium hydroxide, barium sulfate, calcium carbonate, titanium oxide, zinc oxide, antimony trioxide, magnesium oxide, talc, montmorillonite, kaolin or An inorganic filler such as bentonite; a metal filler such as aluminum, gold, silver, copper or nickel. Among them, in terms of dispersibility, cerium oxide, aluminum oxide or aluminum hydroxide is preferred. In particular, the hydrophobic cerium oxide whose stanol group on the surface of the cerium oxide surface is modified with halogenated decane can reduce the water absorption and is suitable for use in the adhesive composition of the present invention.

The amount of the filler (C) is preferably 0.1 to 100 parts by weight, more preferably 0.2 to 50 parts by weight, per 100 parts by weight of the polyurethane polyurea resin (A).

In the adhesive composition (I) of the present invention, a decane coupling agent, a heat stabilizer, a pigment, a dye, an adhesive resin, and a plastic can be blended in a range in which adhesion and heat resistance and storage stability are not deteriorated. Agent, UV absorber, antifoaming agent, or leveling agent.

Further, by using a heat-resistant stabilizer in combination, it is possible to impart more excellent solder heat resistance. As the heat-resistant stabilizer, for example, a hindered phenol-based, phosphorus (phosphite)-based, lactone-based, hydroxylamine-based or sulfur-based material can be used, but it is particularly effective as a hindered phenol-based heat-resistant stabilizer.

Next, an adhesive sheet relating to the present invention will be described.

The adhesive sheet of the present invention has a curable adhesive layer (II) composed of the adhesive composition (I) of the present invention on a release sheet, that is, an adhesive having an uncured adhesive layer (II). Tablets. The curable adhesive layer (II) carried by the first release sheet can be coated thereon with another peelable sheet (second release sheet), and thus, in the adhesive sheet of the present invention The two-layer structure of the release sheet/curable adhesive layer (II) or the three-layer structure of the first release sheet/curable adhesive layer (II)/second release sheet.

When the peelable sheet is used in any of the first release sheet or the second release sheet, it is applied to a flexible printed wiring board substrate, a glass epoxy board, or a stainless steel sheet (for example, SUS board). When the adhesive layer (II) is bonded, it may be peeled off by the adhesive layer, and is not particularly limited. A plastic film such as polyester, polyolefin, polyimide or polyamide may be used; cellophane; or polyethylene laminated paper. Alternatively, the coating agent is applied as a release agent containing a polyfluorene oxide or a fluorine compound.

The adhesive layer (II) is attached to at least one side of the release sheet by conventionally known methods such as knife coating, rigid coating, slit coating, roll coating, curtain coating, bar coating, and photography. After applying the adhesive composition (I) of the present invention by gravure printing, flexographic printing, dip coating, spray coating or spin coating, the adhesive composition (I) does not harden, that is, It is usually produced by drying at 40 to 150 ° C for 20 seconds to 60 minutes.

Further, the dry film thickness of the curable adhesive layer (II) is preferably 5 μm to 500 μm in terms of sufficient adhesion and solder heat resistance, or from the viewpoint of ease of handling, and more preferably 10 μ m to 100 μ m.

Next, a flexible material with an adhesive layer and a flexible printed wiring board with a reinforcing material for the flexible printed wiring board of the present invention will be described.

The reinforcing material with an adhesive layer of the present invention is formed on the reinforcing material to form a curable adhesive layer (II) formed of the above-described adhesive composition (I) of the present invention.

For example, the adhesive composition (I) is applied to the reinforcing material by the method exemplified in the method for producing the above-mentioned release sheet, and dried under the condition that the adhesive composition (I) does not harden. Then, a hardenable adhesive layer (II) can be formed.

The flexible printed wiring board used in the present invention is not particularly limited, and examples thereof include those having a conductive circuit on one surface, a conductive circuit on both surfaces, and a conductive circuit in the interior thereof. Further, the matrix film of the flexible printed wiring board is not particularly limited, and a plastic film having insulating properties, flexibility, and heat resistance is suitable, and examples thereof include polyimine and polyethylene terephthalate. PET), polythiobenzene, polyether oxime, polyetheretherketone, linaloamine, polycarbonate, polyarylate, liquid crystal polymer represented by wholly aromatic polyamine or wholly aromatic polyester. As the copper foil, an electrolytic copper foil or a rolled copper foil can be used.

Examples of the reinforcing material include a glass epoxy board, a metal plate such as aluminum or stainless steel (for example, SUS), or a plate member such as polyimide. The thickness of the reinforcing material is preferably a reinforcing function for a flexible printed wiring board, and is preferably about 20 to 5000 μm.

The flexible printed wiring board with the reinforcing material of the present invention is used for the flexible printed wiring board, using the adhesive composition (I) of the present invention and the adhesive sheet of the present invention, and the glass epoxy board and the metal sheet are used. The reinforcing material such as a polyimine plate or the like is adhered or fixed by an operation of heat lamination, heat pressing, and/or heat hardening alone or in combination.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view schematically showing an aspect of a configuration of a flexible printed wiring board with a reinforcing material according to the present invention. In other words, the flexible printed wiring board 10 with the reinforcing material includes the flexible printed wiring board 11 and the reinforcing member 12. The flexible printed wiring board 11 carries the conductive circuit 2 on one side surface of the insulating base film 1. The reinforcing member 12 is adhered and fixed to the portion of the carrying surface of the conductive film 2 of the substrate film 1 and the portion of the reverse side surface (inside) 11a through the adhesive layer 4. Further, the reinforcing member 12 may be fixed to the entire inner surface 11a of the flexible printed wiring board 11.

A flexible printed wiring board with a reinforcing material can be obtained by various methods.

For example, the adhesive composition (I) is applied to the reinforcing material as described above, and the curable adhesive layer (II) is dried, and the reinforcing material with the curable adhesive layer is prepared, and the adhesive is attached thereto. The hardenable adhesive layer (II) of the reinforcing material of the layer is heated while being in contact with a portion of the conductive circuit in which the flexible printed wiring board is not provided, or is heated after contact bonding, and the hardenable adhesive layer (II) is hardened. Then, the flexible printed wiring board with the reinforcing material of the present invention can be obtained.

Alternatively, the adhesive composition (I) is applied to a portion of the flexible printed wiring board where no conductive circuit is provided, and dried, and the curable adhesive layer (II) is provided, and then the curable adhesive layer ( II) The flexible printed wiring board with the reinforcing material of the present invention can also be obtained by contacting the reinforcing material and heating it or heating it after contact to harden the curable adhesive layer (II).

Further, a flexible printed wiring board with a reinforcing material can also be obtained by using the adhesive sheet of the present invention.

That is, the curable adhesive layer (II) of the adhesive sheet of the present invention having the curable adhesive layer (II) formed of the adhesive composition (I) is brought into contact with the reinforcing material on the release sheet, and secondly, The peelable sheet is peeled off, and the exposed curable adhesive layer (II) is heated while being in contact with a portion of the flexible printed wiring board where no conductive circuit is provided, or heated after contact, or hardened by the adhesive sheet. The adhesive layer (II) contacts the portion of the flexible printed wiring board where the conductive circuit is not provided, and then peels off the peelable sheet, and exposes the exposed curable adhesive layer (II) to the reinforcing material while heating, or After the contact is heated and the curable adhesive layer (II) is cured, the flexible printed wiring board with the reinforcing material of the present invention can also be obtained.

Alternatively, the adhesive sheet (II) formed of the adhesive composition (I) and the adhesive sheet of the present invention on which the other release sheet is laminated are peeled off from the release sheet, and the release sheet is peeled off. The exposed curable adhesive layer (II) is in contact with the reinforcing material, and secondly, the other peelable sheet is peeled off, and the exposed curable adhesive layer (II) is brought into contact with the portion of the flexible printed wiring board where the conductive circuit is not provided. Heating at the same time, or heating after contact, or peeling off a peelable sheet from the adhesive sheet, and contacting the exposed hardenable adhesive layer (II) to a portion of the flexible printed wiring board where no conductive circuit is provided, and secondly The other peelable sheet is peeled off, and the exposed curable adhesive layer (II) is brought into contact with the reinforcing material and heated, or the cured adhesive layer (II) is cured by heating after contact, and the present invention may be obtained. Flexible printed wiring board for reinforcing materials.

Further, the method of applying the adhesive composition (I) can be similarly exemplified by the method described in the method of applying the adhesive sheet.

In either case, the pressure may be applied when the reinforcing material is attached to the flexible printed wiring board and/or after the attachment. More specifically, by laminating the flexible printed wiring board/curable adhesive layer (II)/reinforcing material between the two heated rolls or by thermally pressing the laminated body, The flexible printed wiring board and the reinforcing material can be more strongly bonded.

Further, after the flexible printed wiring board and the reinforcing member are bonded together, the cured adhesive layer (II) can be further cured by heating.

For example, when the curable adhesive layer (II) is heated at 100 to 200 ° C for about 30 minutes to 24 hours, the hardened adhesive layer (III) can be formed. The thickness of the hardened adhesive layer (III) is preferably 5 μm to 100 μm, and more preferably 10 μm to 50 μm.

The flexible printed wiring board with the reinforcing material obtained by the above treatment is passed through the cured adhesive layer (III) to form a state in which the flexible printed wiring board and the reinforcing member are laminated.

Next, a plastic film with a curable adhesive layer and a flexible printed wiring board with a cover film of the present invention will be described.

The plastic film with a curable adhesive layer of the present invention is suitable for use in the manufacture of a flexible printed wiring board with a cover film, and is sandwiched between a plastic film and a protective film which are not peeled off. The curable adhesive layer (II) formed by the adhesive composition (I) of the present invention is obtained.

The plastic film with the curable adhesive layer of the present invention is coated on the plastic film or the protective film which has been subjected to the peeling treatment by various methods of the adhesive composition (I), and dried to form a hardenable adhesive. The agent layer (II) can be obtained by laminating the protective film (II) with a protective film or a plastic film which has not been subjected to release treatment.

The coating method of the adhesive composition (I) may be a method exemplified in the method for producing the peelable sheet, and the like, and dried in the same manner to form a curable adhesive layer (II).

The above-mentioned unpeeled plastic film is a cover film for covering a conductive circuit of a flexible printed wiring board. The plastic film which has not been subjected to the release treatment may be a plastic film such as polyester, polyolefin, polyimide or polyamide, and a polyimide film is preferred.

Further, the protective film referred to herein is a hardenable adhesive layer for protecting a plastic film having a curable adhesive layer, and may be subjected to a peeling treatment or a peeling treatment. In other words, when the protective film is a conductive circuit in which a flexible printed wiring board is coated with a plastic film having a curable adhesive layer, the peeling of the plastic film to which the curable adhesive layer is attached is not particularly It is also possible to use a stripping agent, and various substances can be used. As a person who has not been subjected to the release treatment, for example, a plastic film such as polyester, polyolefin, polyamide or polyamide may be used as a coating agent which is coated with a release agent containing polyfluorene oxide or a fluorine compound.

The flexible printed wiring board with a cover film of the present invention is formed on the side of the conductive circuit side of the flexible printed wiring board having a conductive circuit on the surface thereof, and is formed by the adhesive composition (I) of the present invention. The hardened adhesive layer (III) is coated with a plastic film that has not been peeled off.

Fig. 2 is a cross-sectional view schematically showing an aspect of the configuration of a flexible printed wiring board with a cover film of the present invention. In other words, the flexible printed wiring board 20 with the cover film is adhered to the surface of the flexible printed wiring board 5 on which the conductive circuit 2 is carried, and the adhesive film layer 4 is cured to adhere and fix the plastic film (cover film) 6. . Further, the flexible printed wiring board 5 carries the conductive circuit 2 through the adhesive layer 4a on one side surface of the insulating base film 1.

Such a flexible printed wiring board with a cover film can be obtained by various methods.

For example, the protective film is peeled off by the plastic film with the curable adhesive layer of the present invention, and the exposed curable adhesive layer (II) is brought into contact with the conductive circuit side of the flexible printed wiring board of the surface conductive circuit. The surface is simultaneously heated, or heated after contact, and the curable adhesive layer (II) is cured to obtain the flexible printed wiring board with the cover film of the present invention.

Further, after the adhesive composition (I) of the present invention is applied and dried on the plastic film which has not been subjected to the release treatment to form the curable adhesive layer (II), the curable adhesive layer (II) is contacted. The surface of the flexible printed wiring board on the side of the conductive circuit is simultaneously heated, or heated after contact, and the hardenable adhesive layer (II) is cured, and the flexible printed wiring with the cover film of the present invention can also be obtained. board.

Further, after the adhesive composition (I) is applied and dried on the surface on the conductive circuit side of the flexible printed wiring board to form the curable adhesive layer (II), the curable adhesive layer is formed ( II) The flexible printed wiring board with the cover film of the present invention can also be obtained by contacting the plastic film which has not been peeled off while heating, or heating after contact, to harden the hardenable adhesive layer (II).

Further, the method of applying the adhesive composition (I) can be similarly exemplified by the method described in the method of applying the adhesive sheet.

In either case, the pressure may be applied when the cover film is bonded to the surface of the flexible printed wiring board on the side of the conductive circuit and/or after bonding. More specifically, the laminate composed of the plastic film/curable adhesive layer (II)/flexible printed wiring board which has not been subjected to the release treatment is passed between the heated two rolls or the laminate is heated. Pressurization allows the cover film to be more strongly attached to the flexible printed wiring board.

Further, after the cover film is attached to the flexible printed wiring board, it is further heated, and the curable adhesive layer (II) can be further cured.

For example, when the curable adhesive layer (II) is heated at 100 to 200 ° C for about 30 minutes to 24 hours, the hardened adhesive layer (III) can be formed. The thickness of the hardened adhesive layer (III) is preferably 5 μm to 100 μm, and more preferably 10 μm to 50 μm.

The flexible printed wiring board with a cover film obtained by the above-described process is transmitted through the cured adhesive layer (III), and the cover film is bonded to the conductive circuit side of the flexible printed wiring board.

Next, a printed wiring board formed by laminating a plurality of conductive circuit layers of the present invention will be described.

The printed wiring board used for forming various layers of the printed wiring board formed by laminating the plurality of conductive circuit layers of the present invention includes those having a conductive circuit on only one surface and a conductive circuit on both sides. Further, in order to provide thinness, light weight, and flexibility, it is preferable to use a flexible printed wiring board having a flexible plastic film as an insulating substrate.

Next, a printed wiring board of the present invention formed by laminating a plurality of conductive circuit layers will be described with reference to Figs. 3 to 5 . The printed wiring board of the present invention in which a plurality of conductive circuit layers are laminated is a printed wiring board having a conductive circuit on one surface of an insulating substrate, or a printed wiring board having a conductive circuit on both surfaces of an insulating substrate, and an adhesive is used. The composition (I) is laminated. 4 shows a printed wiring board (hereinafter referred to as a single-sided printed wiring board) 41 having a conductive circuit 2 on one surface of a substrate film 1 as an insulating substrate, and FIG. 5 shows two substrates 1 as an insulating substrate. A printed wiring board (hereinafter referred to as a double-sided printed wiring board) 51 having conductive circuits 2 and 2 on the surface is provided.

[1] of FIG. 3 schematically shows the surface on the conductive circuit side of the first single-sided printed wiring board 41 and the surface on the conductive circuit side of the second single-sided printed wiring board 41, through the adhesive composition (I) The formed hardened adhesive layer 4 is bonded and laminated.

[2] of FIG. 3 schematically shows the surface of one of the double-sided printed wiring board 51 and the surface of the conductive circuit side of the single-sided printed wiring board 41, and the hardened adhesive layer 4 formed by the adhesive composition (I). The state of lamination and lamination.

[3] of FIG. 3 schematically shows the surface of the first single-sided printed wiring board 41 on the side of the conductive circuit and the surface of the second single-sided printed wiring board 41 on which the conductive circuit is not provided, through the adhesive composition (I) The formed adhesive layer 4 is bonded and laminated.

[4] of FIG. 3 schematically shows the surface of one of the double-sided printed wiring board 51 and the surface of the single-sided printed wiring board 41 on which the conductive circuit is not provided, and the hardened adhesive layer 4 formed by the adhesive composition (I). The state of fit and laminate.

[5] of FIG. 3 schematically shows one surface of the first two-sided printed wiring board 51 and one surface of the second double-sided printed wiring board 51, which are pasted by the hardened adhesive layer 4 formed of the adhesive composition (I). Combined, laminated state.

[6] of FIG. 3 schematically shows the surface of the first single-sided printed wiring board 41 on which the conductive circuit is not provided and the surface of the second single-sided printed wiring board 41 on which the conductive circuit is not provided, through the adhesive composition ( I) A state in which the hardened adhesive layer 4 formed is bonded and laminated.

In addition, in FIG. 3, depending on the type of the printed wiring board to be laminated, there is a case where there is no adhesive layer between the insulating substrate (substrate film) of each printed wiring board and the conductive circuit, but In FIGS. 3 to 5, the illustration of the adhesive layer between the insulating substrate of the printed wiring board and the conductive circuit is omitted.

Each of the laminates of the above [1] to [6] in Fig. 3 may be laminated by any combination of the hardened adhesive layers (III), and may be further formed into a multilayer laminate.

The printed wiring board of the laminated composite conductive circuit layer of the present invention can be applied to various methods such as a method of applying the adhesive sheet of the present invention, a method of applying the adhesive composition (I) to a printed wiring board for lamination, and the like. The method is available.

First, the adhesive sheet of the present invention comprising the curable adhesive layer (II) composed of the exfoliable sheet-on-layer adhesive composition (I) and the other releasable sheet laminated thereon may be laminated. A method of manufacturing a printed wiring board formed by a plurality of conductive circuit layers.

The peelable sheet is peeled off from the adhesive sheet, and the exposed curable adhesive layer (II) is brought into contact with the surface of the first single-sided printed wiring board 41 on the side of the conductive circuit, and then the other peelable sheet is peeled off. The exposed curable adhesive layer (II) can be obtained by contacting the surface of the second single-sided printed wiring board 41 on the side of the conductive circuit and adhering thereto, and/or heating after contact bonding. A printed wiring board having a plurality of conductive circuit layers in the laminated state of [1].

The printed wiring board formed by laminating a plurality of conductive circuit layers in the laminated state of [2] in Fig. 3 is a peelable sheet peeled off from the adhesive sheet, and the exposed curable adhesive layer (II) and both sides are exposed. One of the printed wiring boards 51 is in surface contact, and the other peelable sheet is peeled off, and the exposed curable adhesive layer (II) is in contact with the surface of the conductive circuit side of the single-sided printed wiring board 41 and adhered thereto, and/or Or, after contact bonding, heating is performed, or a peelable sheet is peeled off from the adhesive sheet, and the exposed curable adhesive layer (II) is brought into contact with the surface of the single-sided printed wiring board 41 on the side of the conductive circuit. Then, the other peelable sheet is peeled off, and the exposed curable adhesive layer (II) is brought into contact with one surface of the double-sided printed wiring board 51 and adhered thereto, and/or adhered to the adhesive, and then heated. .

The printed wiring board formed by laminating a plurality of conductive circuit layers in the laminated state of [3] in Fig. 3 is a peelable sheet which is peeled off from the adhesive sheet, and the exposed curable adhesive layer (II) and the first The surface of the single-sided printed wiring board 41 on the side of the conductive circuit is contacted, and the other peelable sheet is peeled off, and the exposed hardened adhesive layer (II) is not electrically connected to the second single-sided printed wiring board 41. The surface of the circuit is adhered, and/or heated after contact, or a release sheet is peeled off from the adhesive sheet to expose the cured adhesive layer (II) and the first single side. The surface of the printed wiring board 41 where the conductive circuit is not provided is in contact with each other, and the other peelable sheet is peeled off, and the exposed curable adhesive layer (II) is in contact with the conductive circuit side of the second single-sided printed wiring board 41. After the surface is adhered and/or adhered to the adhesive, it can be obtained by heating.

The printed wiring board formed by laminating a plurality of conductive circuit layers in the laminated state of [4] in Fig. 3 is formed by peeling off a peelable sheet through the self-adhesive sheet, and contacting the exposed curable adhesive layer (II) with On the surface of one of the double-sided printed wiring boards 51, the other peelable sheet-like substrate is peeled off, and the exposed curable adhesive layer (II) is in contact with the surface of the single-sided printed wiring board 41 on which the conductive circuit is not provided. After being adhered and/or adhered to the adhesive, heating is performed, or a peelable sheet is peeled off from the adhesive sheet, and the exposed hardened adhesive layer (II) and the single-sided printed wiring board 41 are not provided with conductive. The surface contact of the circuit is followed by peeling off the other peelable sheet, and the exposed curable adhesive layer (II) is in contact with one surface of the double-sided printed wiring board 51 and adhered thereto, and/or adhered to the contact side. It can be obtained by heating.

The printed wiring board formed by laminating a plurality of conductive circuit layers in the laminated state of [5] in Fig. 3 is formed by peeling off a peelable sheet through the self-adhesive sheet, and contacting the exposed curable adhesive layer (II) with The surface of one of the first two-sided printed wiring board 51 is second, and the other peelable sheet is peeled off, and the exposed hardenable adhesive layer (II) is in contact with one surface of the second double-sided printed wiring board 51 and adhered thereto, and/or It can be obtained by heating after contact sticking.

The printed wiring board formed by laminating a plurality of conductive circuit layers in the laminated state of [6] in Fig. 3 is a peelable sheet which is peeled off from the adhesive sheet, and the exposed curable adhesive layer (II) and the first The surface of one single-sided printed wiring board 41 is not provided with a conductive circuit, and the other peelable sheet is peeled off, and the exposed hardened adhesive layer (II) is not provided to contact the second single-sided printed wiring board 41. The surface of the conductive circuit can be obtained by adhering to the surface and adhering it to the adhesive.

The printed wiring board having a plurality of conductive circuit layers in the laminated state shown in [1] to [6] of FIG. 3 can also be coated on the printed wiring board by the adhesive composition (I) of the present invention. Acquired.

For example, the printed wiring board formed by laminating the plurality of conductive circuit layers in the laminated state of [1] of FIG. 3 can apply the adhesive composition to the surface on the conductive circuit side of the first single-sided printed wiring board 41. (I), drying is performed to form a curable adhesive layer (II), and the curable adhesive layer (II) is in contact with the surface of the second single-sided printed wiring board 41 on the side of the conductive circuit and adhered thereto, and/or Or after contact sticking, it can be obtained while heating.

The printed wiring board formed by laminating a plurality of conductive circuit layers in the laminated state of [2] of FIG. 3 can be dried by applying an adhesive composition (I) to one surface of the double-sided printed wiring board 51 to form a hardened layer. The adhesive layer (II) is heated while being adhered to the surface of the conductive circuit side of the single-sided printed wiring board 41 and adhered to the adhesive layer (II). Alternatively, the adhesive composition (I) is applied to the conductive circuit side of the single-sided printed wiring board 41, and dried to form a curable adhesive layer (II), and the curable adhesive layer (II) is in contact with both sides. One of the printed wiring boards 51 is adhered to the surface, and/or adhered to the adhesive, and then obtained by heating.

The printed wiring board formed by laminating a plurality of conductive circuit layers in the laminated state of [3] of FIG. 3 can be coated with an adhesive composition on the surface of the conductive circuit side of the first single-sided printed wiring board 41 (I). Drying to form a curable adhesive layer (II), and the curable adhesive layer (II) is in contact with the surface of the second single-sided printed wiring board 41 on which the conductive circuit is not provided, and is adhered, and/or After the contact is adhered, heating is performed, or the adhesive composition (I) is applied to the surface of the first single-sided printed wiring board 41 where the conductive circuit is not provided, and dried to form a curable adhesive layer (II). The curable adhesive layer (II) is obtained by being heated while being in contact with the surface of the second single-sided printed wiring board 41 on the side of the conductive circuit and pasted, and/or adhered to the contact.

The printed wiring board formed by laminating a plurality of conductive circuit layers in the laminated state of [4] of FIG. 3 can be dried by applying an adhesive composition (I) to one surface of the double-sided printed wiring board 51. The adhesive layer (II) is heated while contacting the surface of the single-sided printed wiring board 41 on which the conductive circuit is not provided and adhered and/or adhered to the adhesive layer (II). Or, the surface of the single-sided printed wiring board 41 on which the conductive circuit is not provided is coated with the adhesive composition (I), and dried to form a curable adhesive layer (II), and the curable adhesive layer (II) When one of the two printed wiring boards 51 is contacted and adhered, and/or adhered to the adhesive, it can be obtained by heating.

The printed wiring board formed by laminating a plurality of conductive circuit layers in the laminated state of [5] of FIG. 3 can be dried by applying an adhesive composition (I) to one surface of the first two-sided printed wiring board 51. The curable adhesive layer (II) is formed, and the curable adhesive layer (II) is heated while being adhered to one surface of the second double-sided printed wiring board 51 and adhered thereto. Acquired.

The printed wiring board formed by laminating the plurality of conductive circuit layers in the laminated state of [6] of FIG. 3 can be coated with an adhesive composition on the surface of the first single-sided printed wiring board 41 where the conductive circuit is not provided ( I), drying to form a curable adhesive layer (II), and contacting the surface of the second single-sided printed wiring board 41 on which the conductive circuit is not provided, and sticking to the curable adhesive layer (II), and / After the contact sticks, it can be obtained while heating.

Further, the method of applying the adhesive composition (I) can be similarly exemplified by the method described in the method of applying the adhesive sheet.

Further, the printed wiring board having the plurality of conductive circuit layers may be used for the adhesive sheet of the present invention having the curable adhesive layer (II) composed of the adhesive composition (I) on the release sheet.

For example, the printed wiring board formed by laminating a plurality of conductive circuits in the laminated state shown in [1] of FIG. 3 can pass through the hardenable adhesive layer (II) on the adhesive sheet and the first single-sided printed wiring board. The surface contact of the conductive circuit side of 41 is followed by peeling off the peelable sheet, and the exposed curable adhesive layer (II) is in contact with the surface of the conductive circuit side of the second single-sided printed wiring board 41 and adhered thereto. / After the contact sticks, it can be obtained while heating.

The printed wiring board formed by laminating a plurality of conductive circuit layers in the laminated state of [2] of FIG. 3 can be in contact with one surface of the double-sided printed wiring board 51 by the hardenable adhesive layer (II) on the adhesive sheet. Then, the peelable sheet is peeled off, and the exposed curable adhesive layer (II) is heated while being adhered to the surface of the conductive circuit side of the single-sided printed wiring board 41 and adhered thereto. Alternatively, the curable adhesive layer (II) on the adhesive sheet is brought into contact with the surface of the single-sided printed wiring board 41 on the side of the conductive circuit, and then the peelable sheet is peeled off, and the exposed curable adhesive layer (II) is exposed. It is obtained by contacting one surface of the double-sided printed wiring board 51 and sticking it, and/or after being adhered and adhered, and heating is performed.

The printed wiring board formed by laminating a plurality of conductive circuit layers in the laminated state of [3] of FIG. 3 can be electrically connected to the first single-sided printed wiring board 41 via the hardenable adhesive layer (II) on the adhesive sheet. The surface contact on the side of the circuit, and then the peelable sheet is peeled off, and the exposed hardenable adhesive layer (II) is in contact with the surface of the second single-sided printed wiring board 41 on which the conductive circuit is not provided and adhered, and/or After the contact is adhered, heating is performed, or the curable adhesive layer (II) on the adhesive sheet is brought into contact with the surface of the first single-sided printed wiring board 41 where the conductive circuit is not provided, and then the peelable sheet is peeled off. The exposed curable adhesive layer (II) is obtained by being heated while being in contact with the surface of the second single-sided printed wiring board 41 on the side of the conductive circuit and pasted, and/or adhered to the contact.

The printed wiring board formed by laminating a plurality of conductive circuit layers in the laminated state of [4] of FIG. 3 can be brought into contact with one surface of the double-sided printed wiring board 51 via the hardenable adhesive layer (II) on the adhesive sheet. Next, the peelable sheet is peeled off, and the exposed curable adhesive layer (II) is heated while being in contact with the surface of the single-sided printed wiring board 41 on which the conductive circuit is not provided and adhered, and/or adhered to the contact. Or, the hardenable adhesive layer (II) and the single-sided printing cloth on the adhesive sheet The surface of the wire plate 41 is not provided with the surface of the conductive circuit, and then the peelable sheet is peeled off, and the exposed hardened adhesive layer (II) is in contact with one surface of the double-sided printed wiring board 51 and adhered thereto, and/or contacted. After sticking, it can be obtained while heating.

The printed wiring board formed by laminating the plurality of conductive circuit layers in the laminated state of [5] of FIG. 3 can be in contact with one of the first two-sided printed wiring board 51 via the hardenable adhesive layer (II) on the adhesive sheet. On the surface, the peelable sheet is peeled off, and the exposed curable adhesive layer (II) is heated while being adhered to one surface of the second printed wiring board 51 and adhered thereto. Acquired.

The printed wiring board formed by laminating the plurality of conductive circuit layers in the laminated state of [6] of FIG. 3 can be brought into contact with the first single-sided printed wiring board 41 via the hardenable adhesive layer (II) on the adhesive sheet. The surface of the conductive circuit is not provided, and the peelable sheet is peeled off, and the exposed curable adhesive layer (II) is in contact with the surface of the second single-sided printed wiring board 41 on which the conductive circuit is not provided, and is adhered to and/or Or after contact sticking, it can be obtained while heating.

In either case, pressure may be applied when the printed wiring boards are bonded and/or after bonding. More specifically, by laminating the laminate of the printed wiring board/curable adhesive layer (II)/printed wiring board between the heated two rolls or by thermally pressing the laminated body, The plurality of conductive circuit layers are more strongly bonded to each other to obtain a printed wiring board.

Moreover, after obtaining a printed wiring board in which a plurality of conductive circuit layers are laminated, the laminate is further heated, and the curable adhesive layer (II) can be further cured.

For example, when the curable adhesive layer (II) is heated at 100 to 200 ° C for about 30 minutes to 24 hours, the hardened adhesive layer (III) can be formed. The thickness of the hardened adhesive layer (III) is preferably 5 μm to 100 μm, more preferably 10 μm to 50 μm.

The number of printed wiring boards to be laminated is two or more, and the adhesive layer (III) is cured to form a printed wiring board in a state of being mostly laminated.

[Examples]

The invention is further illustrated by the following examples, but the invention is not limited thereto. In the examples, the parts and % respectively mean parts by weight and % by weight, Mn means an average molecular weight, and Mw means a weight average molecular weight.

[Synthesis Example 1]

A polyester polyol obtained from terephthalic acid and adipic acid and 3-methyl-1,5-pentanediol is placed in a reaction vessel equipped with a stirrer, a thermometer, a reflux cooler, a dropping device, and a nitrogen conduit. [Kuraray Polyol P-2011, manufactured by Kuraray Co., Ltd., Mn = 2040] 195.2 parts, 6.67 parts of dimethylolbutanoic acid, 40.7 parts of isophorone diisocyanate, and 70.0 parts of toluene, under a nitrogen atmosphere of 90 After reacting at ° C for 4 hours, 250 parts of toluene was added thereto to obtain an ethyl carbamate prepolymer containing an isocyanate group (Mw = 21,000; relative to the diol compound (c) derived from the polyol compound (a) and having a carboxyl group The hydroxyl group, the molar ratio of the isocyanate group derived from the organic diisocyanate (b) is 1.30).

Next, the above-mentioned ethyl urethane prepolymer solution containing an isocyanate group is added to a mixture of 6.08 parts of isophoronediamine, 0.59 parts of di-n-butylamine, 112.5 parts of 2-propanol and 184.5 parts of toluene. 506.3 parts, reacted at 85 ° C for 4 hours, diluted with 63.0 parts of toluene and 27.0 parts of 2-propanol to obtain a polyurethane polyurea resin (Mw = 110,000; acid value = 10.1 mg KOH / g; relative to having isocyanate) The isocyanate group of the urethane prepolymer (d), the molar ratio of the total amine group is 0.993; the proportion of the amine group derived from the polyamine compound is 94.0 mol% relative to the total amine group; It was 0.85 mgKOH/g; solid solution was about 25%) of solution A-1.

[Synthesis Examples 2 to 5, 7 to 9, 13 and 16]

The reaction was carried out in the same manner as in Synthesis Example 1 except that the materials shown in Table 1 were used, and solutions A-2 to A-5, A-7 to A-9, and A-13 of the polyurethane polyurea resin were obtained. A-16. The properties of the obtained polyurethane polyurea resin are shown in Table 2.

[Synthesis Example 6]

In the same reaction vessel as in Synthesis Example 1, a polyester polyol obtained from terephthalic acid and adipic acid and 3-methyl-1,5-pentanediol was charged [Kuraray Polyol P-made by KURARAY Co., Ltd. 2011", Mn = 2040] 482.9 parts, 16.5 parts of dimethylolbutanoic acid, 100.6 parts of isophorone diisocyanate and 70.0 parts of toluene, reacted at 90 ° C for 4 hours under a nitrogen atmosphere, and added 330.0 parts of toluene thereto. A solution of an ethyl carbamate prepolymer containing an isocyanate group was obtained. The properties of the obtained isocyanate group-containing ethyl urethane prepolymer are shown in Table 2.

[Synthesis Example 10]

In the same reaction vessel as in Synthesis Example 1, 13.30 parts of dimethylolbutanoic acid, 140.0 parts of isophorone diisocyanate, and 200.0 parts of toluene were charged, and the mixture was reacted at 90 ° C for 2 hours under a nitrogen atmosphere, and N was added thereto. 120 parts of N-dimethylacetamide gave a mixed solution of a hydroxy group-added isophorone diisocyanate of dimethylol butyric acid and isophorone diisocyanate.

Next, in the mixture of 74.46 parts of isophoronediamine, 12.56 parts of di-n-butylamine, and 297 parts of 2-propanol, the above-mentioned hydroxyl addition of isophorone to dimethylolbutyric acid is slowly added. 426.0 parts of a mixed solution of a diisocyanate product and isophorone diisocyanate, reacted at 50 ° C for 2 hours, then at 70 ° C for 2 hours, and diluted with 63.0 parts of toluene and 27.0 parts of 2-propanol to obtain a polyamine group. A solution of a mixture of a formate polyurea resin and a polyurea resin A-10. The properties of the mixture of the obtained resins are shown in Table 2. Further, the solid component of A-10 was insoluble in tetrahydrofuran (THF), and thus the weight average molecular weight could not be determined.

[Synthesis Example 11]

In the same reaction vessel as in Synthesis Example 1, a polyester polyol obtained from terephthalic acid and adipic acid and 3-methyl-1,5-pentanediol was charged [Kuraray Polyol P-made by KURARAY Co., Ltd. 2011", Mn = 2040] 189.7 parts, 5.96 parts of dimethylol butyric acid, 29.3 parts of isophorone diisocyanate and 35.0 parts of toluene, reacted at 90 ° C for 10 hours under a nitrogen atmosphere, and added 185.0 parts of toluene thereto. Further, 55.0 parts of 2-propanol was diluted to obtain a solution A-11 of a polyurethane resin (Mw = 88,000, an acid value = 10.0 mgKOH/g, an amine value of 0 mgKOH/g, and a solid content of about 45%).

[Synthesis Example 12]

In the same reaction vessel as in Synthesis Example 1, a polyester polyol obtained from terephthalic acid and adipic acid and 3-methyl-1,5-pentanediol was charged [Kuraray Polyol P-made by KURARAY Co., Ltd. 2011", Mn = 2040] 189.2 parts, 5.94 parts of dimethylol butyric acid, 29.8 parts of isophorone diisocyanate and 35.0 parts of toluene, reacted at 90 ° C for 10 hours under a nitrogen atmosphere, and added 185.0 parts of toluene thereto. Further, 55.0 parts of 2-propanol was diluted to obtain a solution A-12 of a polyurethane resin (Mw = 91,000, an acid value = 10.0 mgKOH/g, an amine value of 0 mgKOH/g, and a solid content of about 45%).

[Synthesis Example 14]

In the same reaction vessel as in Synthesis Example 1, a polyester polyol obtained from terephthalic acid and adipic acid and 3-methyl-1,5-pentanediol was charged [Kuraray Polyol P-made by KURARAY Co., Ltd. 2011", Mn = 2040] 190.1 parts, 6.80 parts of dimethylol butyric acid, 43.3 parts of isophorone diisocyanate and 70.0 parts of toluene, reacted at 90 ° C for 4 hours under a nitrogen atmosphere, and added 250 parts of toluene thereto. A solution of an ethyl carbamate prepolymer containing an isocyanate group was obtained.

Next, in the mixture of 7.96 parts of isophoronediamine, 0.91 part of di-n-butylamine, 112.5 parts of 2-propanol and 184.5 parts of toluene, the above-mentioned ethyl urethane prepolymer containing isocyanate group was added. 504.1 parts of the solution was reacted at 50 ° C for 2 hours, followed by reaction at 70 ° C for 2 hours, and diluted with 63.0 parts of toluene and 27.0 parts of 2-propanol to obtain a polyurethane polyurea resin solution A-14. The properties of the mixture of the obtained resins are shown in Table 2.

[Synthesis Example 15]

The polyurethane was reacted in the same manner as in Synthesis Example 14 except that the materials shown in Table 1 were used to obtain a polyurethane urethane resin solution A-15. The properties of the obtained polyurethane polyurea resin are shown in Table 2.

Further, the number average molecular weight (Mn) of the polyol compound, the weight average molecular weight (Mw) of the urethane prepolymer and the polyurethane polyurea resin are converted into polyphenylbenzene by GPC measurement. The number average molecular weight and the weight average molecular weight of ethylene are as follows.

Device: Shodex GPC System-21 [Showa Electric Co., Ltd.] column: A total of three Shodex KF-802, KF-803L, and KF-805L [Showa Electric Co., Ltd.] are connected for use.

Solvent: tetrahydrofuran (THF) flow rate: 1.0 mL/min Temperature: 40 ° C Sample concentration: 0.2% by weight Sample injection amount: 100 μL

In Table 1, the abbreviation of the type of the polyol compound (a) is as follows. P-2011: Polyester polyol obtained from terephthalic acid and adipic acid and 3-methyl-1,5-pentanediol [Kuraray Polyol P-2011, manufactured by KURARAY Co., Ltd., Mn = 2040].

PTG-2000SN: Polyoxytetramethylene glycol [PTG-2000SN, manufactured by Hodogaya Chemical Industry Co., Ltd., Mn = 2029].

CD220: polyhexamethylene carbonate diol [Proxel CD220, manufactured by Daicel Chemical Industry Co., Ltd., Mn = 1965].

[Example 1]

With respect to 400 parts of solution A-1 of the polyurethane polyurethane resin obtained in Synthesis Example 1, tetrakis(epoxypropyloxyphenyl)ethane ("EPIKOTE 1031S" manufactured by Japan Epoxy Resin Co., Ltd.) was mixed. Epoxy equivalent = 180 to 220 g/eq) 10 parts and 20 parts of a hydrophobic ceria filler ("Nipsil SS-50F" manufactured by Seisaku Silica Co., Ltd.] to obtain an adhesive composition.

The adhesive composition was applied to a polyimide film having a thickness of 75 μm by a dry film thickness of 25 μm, and dried at 80 ° C for 2 minutes to form a layer of a hardenable adhesive layer (II). Polyimine reinforcement.

Further, the above-mentioned adhesive composition was applied to a polyimide film having a thickness of 25 μm [manufactured by Toray Industries, KAPTON 100H] so as to have a dry film thickness of 25 μm, and dried at 80 ° C for 2 minutes. A cover film with a curable adhesive layer was prepared by attaching a protective film to the adhesive surface (a PET film treated by a polyoxynitride).

Further, the above-mentioned adhesive composition was applied to the release-treated polyester film so as to have a dry film thickness of 25 μm to form a curable adhesive layer (II), which was laminated and subjected to another release treatment. The polyester film is used to form an adhesive sheet in which the curable adhesive layer (II) is sandwiched by the peelable sheet-like substrate.

[Examples 2 to 5 and Comparative Examples 1 to 2, 5 to 12, 14 to 16]

An adhesive composition was prepared in the same manner as in Example 1 except that a solution of a polyurethane urethane resin of the type and amount shown in Table 3, an epoxy resin, and a filler was used, and a layer of a curable adhesive was attached ( II) Polyimine reinforcing material, a cover film with a curable adhesive layer, and an adhesive sheet.

[Comparative Example 3]

Nitrile butadiene rubber containing carboxyl group [Nipol 1072J, manufactured by Zeon Co., Ltd., combined with 27.0% acrylonitrile, viscosity 48] 100 parts, bisphenol A epoxy resin [made by Japan Epoxy Resin Co., Ltd." EPIKOTE 828", epoxy equivalent = 189g/eq] 200 parts, anhydrous cerium oxide filler [Aerosil 300" manufactured by Nippon Aerosil Co., Ltd.] 2 parts, finely pulverized dicyandiamide [Japan Epoxy Resin Co., Ltd. "Epikure DICY7"] 14 parts and 2 parts of an imidazole-based hardening accelerator [Amicure PN-40" by Ajinomoto Fine Techno Co., Ltd., dissolved in toluene to a solid content of 30%, and an adhesive composition was prepared. . Using the obtained adhesive composition, a polyimide film with a curable adhesive layer (II), a cover film with a curable adhesive layer, and an adhesive sheet were prepared in the same manner as in Example 1.

[Comparative Example 4]

In the same reaction apparatus as in Synthesis Example 1, 95.0 parts of butyl acrylate, 5.0 parts of acrylic acid, 163.0 parts of ethyl acetate, and 0.06 parts of 2,2'-azobisisobutyronitrile were charged, and the air in the reaction container was set. After the replacement with nitrogen, the reaction solution was heated to 80 ° C while stirring for 9 hours while stirring in a nitrogen atmosphere. After the completion of the reaction, 57 parts of toluene was added to obtain an acrylic resin solution having a solid content of 30.0%.

133 parts of the acrylic resin solution, 10 parts of bisphenol A type epoxy resin "EPIKOTE 828", 0.1 part of cerium oxide filler "Aerosil 300", and 0.7 parts of finely pulverized dicyandiamide "EPIKOTE DICY7" and imidazole type 0.1 part of the hardening accelerator "Amicure PN-40" was obtained, and the adhesive composition was obtained. Using the obtained adhesive composition, a polyimide film with a curable adhesive layer (II), a cover film with a curable adhesive layer, and an adhesive sheet were prepared in the same manner as in Example 1.

[Comparative Example 5]

167 parts of the urethane prepolymer resin obtained in Synthesis Example 6 was mixed with bisphenol A type epoxy resin [EPIKOTE 1001 manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent = 450 to 500 g/eq] 20 parts, diaminobiphenyl hydrazine ["Sekacure-S" manufactured by Wakayama Seiki Co., Ltd.] 8 parts and hydrophobic cerium oxide filler [Nipsil SS-50F" manufactured by Tosoh Silica Co., Ltd. 30 A part of the adhesive composition. Using the obtained adhesive composition, a polyimide film with a curable adhesive layer (II), a cover film with a curable adhesive layer, and an adhesive sheet were prepared in the same manner as in Example 1.

[Comparative Example 13]

With respect to the A-13400 parts of the solution of the polyurethane polyurea resin obtained in Synthesis Example 13, tetrakis(epoxypropyloxyphenyl)ethane ("EPIKOTE 1031S" manufactured by Japan Epoxy Resin Co., Ltd.) was mixed. Oxygen equivalent = 180~220g/eq) 10 parts, 2.5 parts of isophordiamine and 20 parts of hydrophobic cerium oxide filler [Nipsil SS-50F" manufactured by Tosoh Silica Co., Ltd. to obtain adhesive composition .

The adhesive composition was applied to a polyimide film having a thickness of 75 μm in a dry film thickness of 25 μm, and dried at 80 ° C for 2 minutes to form a layer of a hardenable adhesive layer (II). Polyimine reinforcement.

Further, the above-mentioned adhesive composition was applied to a polyimide film having a thickness of 25 μm to a thickness of 25 μm [manufactured by Toray Industries, KAPTON 100H], and dried at 80 ° C for 2 minutes. A protective film (PET film subjected to release treatment by polyfluorene oxide) was attached to the adhesive surface to prepare a cover film with a curable adhesive layer.

Further, the above-mentioned adhesive composition was applied to the release-treated polyester film so as to have a dry film thickness of 25 μm to form a curable adhesive layer (II), which was laminated and subjected to another release treatment. The polyester film is used to form an adhesive sheet in which the curable adhesive layer (II) is sandwiched by the peelable sheet-like substrate.

[Comparative Example 17]

In the same manner as in Example 1, except that a trimeric isocyanate of hexamethylene diisocyanate ("SUMIDULE N3300" manufactured by Bayer Urethane Co., Ltd., NCO% = 21.8%) was used as the epoxy resin instead of the epoxy resin. The adhesive composition, the polyimide reinforced material with the curable adhesive layer (II), the cover film with the curable adhesive layer, and the adhesive sheet.

[Comparative Example 18]

The same example as the crosslinking agent except that the alkylated melamine resin (CYMEL 303 manufactured by Mitsui Cytec Co., Ltd. and the hardening catalyst (Catalyst 600, 0.5 phr for melamine resin)) was used as the crosslinking agent instead of the epoxy resin. (1) A pressure-sensitive adhesive composition, a polyimide-based reinforcing material with a curable adhesive layer (II), a cover film with a curable adhesive layer, and an adhesive sheet are prepared.

[Comparative Example 19]

In addition to replacing epoxy resin, use ginseng-2,4,6-(1-吖 )-1,3,5-three In addition to the crosslinking agent, the adhesive composition, the polyimine reinforcing material with the curable adhesive layer (II), the cover film with the curable adhesive layer, and the adhesive sheet were prepared in the same manner as in Example 1. .

[Comparative Example 20]

The adhesive composition was prepared in the same manner as in Example 1 except that the EPIKOTE 1031S which is an epoxy resin was used, and the polyiminoimide reinforcing material with the curable adhesive layer (II) was attached, and the hardenable adhesive layer was attached. Cover film and adhesive sheet.

In Table 3, the abbreviations of the types of the epoxy resin (B), the filler (C), and the crosslinking agent other than the epoxy resin are shown as follows.

EP1031S: Tetrakis(epoxypropyloxyphenyl)ethane, "EPIKOTE 1031S" manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent = 180~220g/eq EP152: phenol novolac type epoxy resin, Japan Epoxy Resin ( EPIKOTE 152, epoxy equivalent = 172~178g/eq EP828: bisphenol A epoxy resin, "EPIKOTE 828" manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent = 189g/eq SS-50F: Hydrophobic cerium oxide filler, "Nipsil SS-50F" R972: a hydrophobic cerium oxide filler, manufactured by Aerosil Co., Ltd., Japan, "AEROSIL R972" TAT: gin-2, 4, 6 -(1-吖 )-1,3,5-three

[Physical evaluation]

The following test was carried out using the adhesive composition obtained in the examples and the comparative examples, the polyimide reinforced material having the curable adhesive layer, the cover film with the curable adhesive layer, and the adhesive sheet.

(1) Polyimine reinforcing material with a hardenable adhesive layer

(1-1) The adhesion strength to the polyimide film is attached to the side of the curable adhesive layer of the polyimide material of the curable adhesive layer (II) and another polyimide film (film thickness) 75 μm) After bonding with a hot laminator having a roll temperature of 100 ° C, it was heat-pressed at 150 ° C, 1.0 MPa, 2 minutes, and heated in an electric furnace at 150 ° C for 180 minutes to prepare a polyimide. A laminate of a reinforcing material/hardened adhesive layer (III)/polyimine film. The laminate was cut into a width of 10 mm, and subjected to a peeling test at 90° peeling at a tensile speed of 50 mm/min under an ambient gas of 23° C. and a relative humidity of 50% to determine the adhesion strength (N/cm).

(1-2) Adhesion strength for aluminum sheets

The adhesive layer side of the polyimine-improving material with the curable adhesive layer (II) and the aluminum plate (thickness 100 μm, which has been subjected to caustic treatment) are bonded together using a heat laminator having a roll temperature of 100 ° C to The mixture was heated under conditions of 150 ° C, 1.0 MPa, and 2 minutes, and heated in an electric furnace at 150 ° C for 180 minutes to prepare a laminate of a polyimide/hardened adhesive layer (III)/aluminum plate. This laminate was cut into a width of 10 mm, and was subjected to 180 at a tensile speed of 50 mm/min under an ambient gas of 23 ° C and a relative humidity of 50%. Peeling test was performed to determine the adhesion strength (N/cm).

(1-3) Preservation of adhesion strength after stability test

The curable adhesive layer-attached protective film (peel-treated PET film) of the above-mentioned polybenzazole having the curable adhesive layer (II) is placed in a thermostat at 40 ° C for 30 days, and the protective film is peeled off. The cured adhesive layer side and another polyimide film (film thickness: 75 μm) were bonded together using a heat laminator having a roll temperature of 100 ° C, and then hot-added at 150 ° C, 1.0 MPa, and 2 minutes. The laminate was heated in an electric furnace at 150 ° C for 180 minutes to prepare a laminate of a polyimide/hardened adhesive layer (III)/polyimine film.

The laminate was cut into a width of 10 mm, and subjected to a peeling test of 90° peeling at a tensile speed of 50 mm/min under an ambient gas of 23% relative humidity of 50% to determine the adhesion strength after storage stability test (N/ Cm).

(1-4) Solder heat resistance after humidification The laminate for the adhesion strength of the aluminum plate described above (polyimide reinforcing material/hardened adhesive layer (III)/laminate laminate) was cut at a width of 10 mm. After immersing in purified water at 85 ° C for 3 hours, the polyiminoimide reinforcing material was immediately contacted with the molten solder at 260 ° C for 1 minute. The appearance was visually observed, and the presence or absence of adhesion abnormalities such as foaming, floating, and peeling of the adhesive layer was evaluated.

○: No adhesion abnormality.

△: A slight adhesion was observed.

×: There is an adhesion abnormality.

The test results are shown in Table 4.

(2) Cover film with a hardenable adhesive layer

(2-1) Adhesion strength to the copper luster surface The protective film with the cover film of the curable adhesive layer is peeled off, and the curable adhesive layer is applied to the rough matte side of the electrolytic copper foil having a thickness of 35 μm. After laminating by a heat laminator having a roll temperature of 100 ° C, the film was heat-pressed at 150 ° C, 1.0 MPa, and 2 minutes, and then heated in an electric furnace at 150 ° C for 180 minutes to prepare an electrolytic copper foil with a cover film. .

The above-mentioned electrolytic copper foil with a cover film was cut into a width of 10 mm, and subjected to 180° peeling between the cover film and the electrolytic copper foil at a tensile speed of 50 mm/min under an ambient gas of 23° C. and a relative humidity of 50%. The peeling test was performed to determine the adhesion strength (N/cm).

(2-2) Solder heat resistance after humidification The above-mentioned electrolytic copper foil with a cover film was cut into a width of 10 mm, immersed in purified water at 85 ° C for 3 hours, and immediately covered with a molten solder on the side of the film at 260 ° C. Contact for 1 minute. The appearance was visually observed, and the presence or absence of adhesion abnormalities such as foaming, floating, and peeling of the adhesive layer was evaluated.

○: No adhesion abnormality.

△: A slight adhesion was observed.

×: There is an adhesion abnormality.

(2-3) Pattern embedding property after storage stability test The cover film with a curable adhesive layer was peeled off by a 40 ° C thermostatic bath for 30 days, and a comb-shaped conductor pattern was formed by subtraction. Flexible copper-clad laminate (line/space 0.1mm), bonded to the hardenable adhesive layer using a thermal laminator with a roll temperature of 100 ° C, and then hot pressed at 150 ° C, 1.0 MPa, 2 minutes. The film was heated in an electric furnace at 150 ° C for 180 minutes to obtain a flexible copper-clad laminate having a comb-shaped conductor pattern with a cover film. The filling property of the cover film adhesive layer to the portion of the comb-shaped conductor pattern was visually observed, and the presence or absence of voids was observed.

○: No gaps.

△: A small gap was observed.

×: Many voids were observed.

(2-4) Change in insulation resistance The protective film was peeled off from the cover film with the curable adhesive layer, and the flexible copper-clad laminate (line/space 0.1 mm) which formed the comb-type conductor pattern by the subtraction method was used. After bonding the curable adhesive layer with a heat laminator having a roll temperature of 100 ° C, it was heat-pressed at 150 ° C, 1.0 MPa, and 2 minutes, and heated in an electric furnace at 150 ° C for 180 minutes to obtain a cover film. A flexible copper-clad laminate having a comb-shaped conductor pattern. A flexible copper-clad laminate having a comb-shaped conductor pattern covering the film was attached, and a voltage of 24 V and 1000 Hrs was applied between the comb-shaped conductors under an ambient gas of 85 ° C and 85% RH (relative humidity). The resistance between the comb-shaped conductors before and after the applied voltage in the humidified ambient gas is compared.

○: Ra/Rb≦10△: Ra/Rb>10

(here, Ra represents the resistance value before the applied voltage, and Rb represents the resistance value after the applied voltage.)

The test results are shown in Table 5.

(3) Adhesive tablets

(3-1) Adhesion strength to the copper roughened surface The adhesive sheet (the thickness of the adhesive layer is 25 μm) is peeled off from the two peelable sheet-like substrates, and the hardenable adhesive layer is sandwiched between the electrolytic layers having a thickness of 35 μm. The rough matte surface of the copper foil and the polyimine film (Capton 200EN) having a thickness of 50 μm are thermally laminated at a drum temperature of 100 ° C, and then hot-added at 150 ° C, 1.0 MPa, and 2 minutes. The pressure was further heated in an electric furnace at 150 ° C for 180 minutes to obtain a laminate composed of a rough matte side of the electrolytic copper foil/hardened adhesive layer (III)/polyimine film.

The laminate was cut into a width of 10 mm, and subjected to a peeling test at 180° peeling at a tensile speed of 50 mm/min under an ambient gas of 23° C. and a relative humidity of 50% to determine the adhesion strength (N/cm).

(3-2) Adhesion strength to the copper shiny surface The two release sheet-like substrates of the adhesive sheet (the thickness of the adhesive layer is 25 μm) are peeled off, and the hardenable adhesive layer is sandwiched by the electrolytic layer having a thickness of 35 μm. The shiny surface of the copper foil and the polyimine film (Capton 200EN) having a thickness of 50 μm were thermally laminated at a drum temperature of 100 ° C, and then hot pressed at 150 ° C, 1.0 MPa, and 2 minutes. Further, the laminate was heated in an electric furnace at 150 ° C for 180 minutes to obtain a laminate comprising a glossy surface of the electrolytic copper foil/hardened adhesive layer (III)/polyimine film.

The laminate was cut into a width of 10 mm, and subjected to a peeling test at 180° peeling at a tensile speed of 50 mm/min under an ambient gas of 23° C. and a relative humidity of 50% to determine the adhesion strength (N/cm).

(3-3) Solder heat resistance after humidification The above-mentioned laminate composed of the rough matte side of the electrolytic copper foil/hardened adhesive layer (III)/polyimine film was cut into a width of 10 mm at 85 mm. After immersing in the refined water of °C for 3 hours, the polyimide film side was immediately contacted with molten solder at 260 ° C for 1 minute. The appearance was visually observed, and the presence or absence of adhesion abnormalities such as foaming, floating, and peeling of the adhesive layer was evaluated.

○: No adhesion abnormality.

△: A slight adhesion was observed.

×: There is an adhesion abnormality.

(3-4) Pattern embedding property after storage stability test The peelable sheet-like substrate of the adhesive sheet (the thickness of the adhesive layer of 25 μm) placed in a 40 ° C thermostatic bath for 30 days was peeled off. A curable adhesive layer is sandwiched between a flexible copper-clad laminate (line/space 0.1 mm) and a 50 μm thick polyimide film (Capton 200EN) formed by subtraction to form a comb-shaped conductor pattern, After the temperature of the drum was 100 ° C, the laminate was heat-pressed at 150 ° C, 1.0 MPa, and 2 minutes, and heated in an electric furnace at 150 ° C for 180 minutes to obtain a comb-shaped conductor pattern with a polyimide film. Flexible copper clad laminate. The filling property of the adhesive layer on the comb-shaped conductor pattern portion was visually observed to investigate whether or not there was a void.

○: No gaps.

△: A small gap was observed.

×: Many voids were observed.

(3-5) Chemical resistance The adhesive composition (I) obtained in each of the examples and the comparative examples was applied to a tinplate with a dry film thickness of 50 μm, and heated at 150 ° C in an electric furnace. It is hardened in minutes to separate the hardened film by mercury amalgam (Amalgam). The appearance of the hardened film after immersion in a 10% NaOH aqueous solution and a 10% hydrochloric acid aqueous solution for 24 hours and the appearance after immersion in acetone for 3 hours were visually observed to evaluate whether it was swollen, dissolved, or the like.

○: No change.

△: A slight change was observed.

×: Obvious changes were observed.

The test results are shown in Table 6.

[Industrial availability]

The adhesive composition of the present invention can be suitably used for lamination of a flexible printed wiring board or assembly of a cover film for protecting a reinforcing material and a conductive circuit.

The present invention has been described above with reference to specific aspects, and variations and modifications that are known to those skilled in the art are included in the scope of the present invention.

1. . . Matrix film

2. . . Conductive circuit

3. . . Reinforcing material

4. . . Hardened adhesive layer (III)

4a. . . Adhesive layer

5. . . Flexible printed wiring board

6. . . Plastic film (cover film)

10. . . Flexible printed wiring board with reinforcing material

11. . . Flexible printed wiring board

11a. . . Inside the flexible printed wiring board

12. . . Reinforcing material

20. . . Flexible printed wiring board

41. . . Second single-sided printed wiring board

51. . . Second two-sided printed wiring board

Fig. 1 is a schematic cross-sectional view showing a flexible printed wiring board on which a reinforcing material having an adhesive layer is attached.

Fig. 2 is a schematic cross-sectional view showing a flexible printed wiring board covered with a cover film with an adhesive layer.

3 [1] to [6] are schematic cross-sectional views of a printed wiring board formed by laminating a plurality of conductive circuit layers.

Fig. 4 is a schematic cross-sectional view showing a single-sided printed wiring board (1).

Figure 5 is a schematic cross-sectional view of a double-sided printed wiring board (2).

1. . . Matrix film

2. . . Conductive circuit

4. . . Hardened adhesive layer (III)

41. . . Second single-sided printed wiring board

51. . . Second two-sided printed wiring board

Claims (34)

An adhesive composition (I) characterized by comprising a polyurethane polyurea resin (A) and an epoxy resin (B), and the polyurethane polyurea resin (A) will be plural The urethane prepolymer (d) having an isocyanate group obtained by reacting the alcohol compound (a), the organic diisocyanate (b) and the diol compound (c) having a carboxyl group, and the polyamine compound (e) and The monoamine-based compound (f) is obtained by reacting under the following conditions, and has a weight average molecular weight of 80,000 to 250,000 and an acid value of 3 to 25 mgKOH/g; (i) an ethyl carbamate prepolymer having an isocyanate group (d) The ratio of the isocyanate group to the amine group of the polyamine compound (e) and the monoamine compound (f) is an amine group/isocyanate group = 0.8/1 to 0.999/1 (mole ratio); and (ii) a polyamine In the total of 100 mol% of the amine group of the base compound (e) and the amine group of the monoamine compound (f), the ratio of the amine group of the polyamine compound (e) is from 90.0 to 97.0 mol%; and having an isocyanate group The urethane prepolymer (d) is obtained by reacting a polyol compound (a) and a hydroxyl group of a diol compound (c) having a carboxyl group with an isocyanate group of an organic diisocyanate (b). The ratio is the range of isocyanate group / hydroxyl group = 1.05 / 1 to 1.50/1 (mole ratio); the ratio of the polyol compound (a) to the diol compound (c) having a carboxyl group is a polyol compound (a) / has Carboxyl group diol compound (c)=95/5~20/80 (mole ratio); containing epoxy resin (B) 5 to 100 with respect to 100 parts by weight of polyurethane urethane resin (A) Parts by weight; and in the synthesis of the above polyurethane polyurethane resin (A), the ester is used. A solvent selected from the group consisting of a solvent, a ketone solvent, a glycol ether solvent, an aliphatic solvent, an aromatic solvent, an alcohol solvent, and a carbonate solvent. The adhesive composition (I) of claim 1, wherein the polyurethane urethane resin (A) has an amine value of 0 to 1.5 mgKOH/g. The adhesive composition (I) of claim 1, wherein the polyol compound (a) has an average molecular weight of from 1,000 to 5,000, and the weight average molecular weight of the ethyl urethane prepolymer (d) is 10000~50000. The adhesive composition (I) of claim 1, wherein the filler (C) is contained. The adhesive composition (I) according to the fourth aspect of the invention, wherein the filler (C) is contained in an amount of 0.1 to 100 parts by weight based on 100 parts by weight of the polyurethane polyurea resin (A). An adhesive sheet characterized by having a curable adhesive layer (II) comprising the adhesive composition (I) of claim 1 in the release sheet. An adhesive sheet according to item 6 of the patent application, wherein the curable adhesive layer (II) has other peelable sheets. A reinforcing material with an adhesive layer for a flexible printed wiring board, characterized in that the reinforcing material has a curable adhesive layer formed of the adhesive composition (I) of claim 1 (II). A flexible printed wiring board with a reinforcing material, characterized in that the portion of the flexible printed wiring board where no conductive circuit is provided is formed by the adhesive composition (I) of the first application of the patent scope Hardened adhesion The agent layer (III) allows the reinforcing material to be fixed. A method for producing a flexible printed wiring board with a reinforcing material, characterized in that the reinforcing sheet is fixed to the flexible printed wiring board using the adhesive sheet of claim 6 of the patent application. A method for producing a flexible printed wiring board with a reinforcing material, characterized in that an adhesive composition (I) of the first application of the patent application is applied to a reinforcing material, and a hardenable adhesive layer (II) is provided. Then, the curable adhesive layer (II) is heated while being in contact with the portion of the flexible printed wiring board where the conductive circuit is not provided, and is adhered and/or adhered to the contact. A plastic film with an adhesive layer, characterized in that a sclerosing adhesive containing the adhesive composition (I) of claim 1 is sandwiched between a plastic film and a protective film which have not been subjected to peeling treatment. Layer (II). A flexible printed wiring board with a cover film, characterized in that a surface of a conductive circuit side of a flexible printed wiring board having a conductive circuit on its surface is formed by an adhesive of the first application of the patent scope The hardened adhesive layer (III) formed of the substance (I) is coated with a plastic film which has not been subjected to peeling treatment. A manufacturing method of a flexible printed wiring board with a cover film, characterized in that the plastic film peeling protective film with an adhesive layer attached to the 12th item of the patent application scope, the exposed hardenable adhesive layer (II) It is heated while being in contact with the surface of the flexible printed wiring board having the conductive circuit on the surface of the conductive circuit and adhering and/or adhering to the contact. A method for producing a flexible printed wiring board with a cover film, characterized in that the adhesive composition (I) of claim 1 is applied to a surface of a plastic film which has not been subjected to peeling treatment to form The curable adhesive layer (II), and secondly, the curable adhesive layer (II), while contacting the surface of the conductive circuit side of the flexible printed wiring board having the conductive circuit on the surface and adhering, and/or After the contact sticks, it is heated. A method of manufacturing a flexible printed wiring board with a cover film, characterized in that the adhesive composition (I) of claim 1 is applied to a flexible printed wiring board having a conductive circuit on its surface The surface of the conductive circuit side forms a hardenable adhesive layer (II), and secondly, the hardened adhesive layer (II) is contacted with the unpeeled plastic film and adhered, and/or adhered to the contact. After that, heat is performed. A printed wiring board formed by laminating a plurality of conductive circuit layers, characterized in that the hardened adhesive layer (III) formed by the adhesive composition (I) of claim 1 of the patent application has only one surface a surface on a conductive circuit side of a first single-sided printed wiring board (1) having a conductive circuit, and a surface on a conductive circuit side of a second single-sided printed wiring board (1) having a conductive circuit on only one surface Or bonding one surface of the double-sided printed wiring board (2) having conductive circuits on both sides to the surface of the conductive circuit side of the single-sided printed wiring board (1) having only one surface having a conductive circuit; The surface of the first single-sided printed wiring board (1) having a conductive circuit on the conductive circuit side and the second single-sided printed wiring board (1) having a conductive circuit on only one surface are not provided with conductivity The surface of the circuit is fitted; Or bonding one surface of the two-sided printed wiring board (2) having conductive circuits on both sides to the surface of the single-sided printed wiring board (1) having only one surface having a conductive circuit, and having no conductive circuit; or a surface of the first two-sided printed wiring board (2) having a conductive circuit is bonded to a surface of the second two-sided printed wiring board (2) having conductive circuits on both sides; or that only one surface has a conductive circuit The surface of the first single-sided printed wiring board (1) on which the conductive circuit is not provided is bonded to the surface of the second single-sided printed wiring board (1) having only one surface having a conductive circuit, and the conductive circuit is not provided. A method for manufacturing a printed wiring board formed by laminating a plurality of conductive circuit layers, characterized in that a peeling sheet is peeled off from an adhesive sheet of claim 7 and an exposed curable adhesive layer is exposed (II And contacting the surface of the first single-sided printed wiring board (1) having a conductive circuit on the surface of the conductive circuit, and secondly peeling off another peelable sheet, and exposing the exposed hardenable adhesive layer (II), The surface of the second single-sided printed wiring board (1) having a conductive circuit on the surface of the conductive circuit is contacted and adhered, and/or adhered to the contact, and heated. A method for manufacturing a printed wiring board formed by laminating a plurality of conductive circuit layers, characterized in that a peeling sheet is peeled off from an adhesive sheet of claim 7 and an exposed curable adhesive layer is exposed (II ), in contact with the surface on the conductive circuit side of the first single-sided printed wiring board (1) having only one surface having a conductive circuit, and secondly peeling off another peelable sheet, The exposed hardenable adhesive layer (II) is contacted with a surface of the second single-sided printed wiring board (1) having a conductive circuit and having no conductive circuit, and is adhered, and/or contacted. After being adhered, heating is performed; or, the adhesive sheet of claim 7 is peeled off, and the peelable sheet is peeled off, and the exposed hardened adhesive layer (II) is exposed to the first single sheet having a conductive circuit on only one surface. The surface printed wiring board (1) is not provided with the surface contact of the conductive circuit, and the other peelable sheet is peeled off, and the exposed curable adhesive layer (II) is contacted with the second single sheet having the conductive circuit on only one surface. The surface of the surface of the printed wiring board (1) on the side of the conductive circuit is adhered and/or heated after being adhered to the contact. A method for manufacturing a printed wiring board formed by laminating a plurality of conductive circuit layers, characterized in that a peeling sheet is peeled off from an adhesive sheet of claim 7 and an exposed curable adhesive layer is exposed (II The surface of the single-sided printed wiring board (1) having only one surface having a conductive circuit is in contact with the surface on the side of the conductive circuit, and the other peeling sheet is peeled off, and the exposed hardened adhesive layer (II) is contacted. a surface of the printed circuit board (2) having two sides of the conductive circuit on both sides and adhered thereto, and/or heated after contact bonding; or peeling off the adhesive sheet from the seventh application of the patent scope a sheet, a surface of one of the exposed hardened adhesive layers (II), and a double-sided printed wiring board (2) having conductive circuits on both sides Contact, and secondly, another peelable sheet is peeled off, and the exposed curable adhesive layer (II) is contacted with the surface of the conductive circuit side of the single-sided printed wiring board (1) having a conductive circuit on one surface and adhered thereto. And/or heating after contact sticking. A method for manufacturing a printed wiring board formed by laminating a plurality of conductive circuit layers, characterized in that a peeling sheet is peeled off from an adhesive sheet of claim 7 and an exposed curable adhesive layer is exposed (II The surface of the single-sided printed wiring board (1) having only one surface having a conductive circuit is not in contact with the surface on which the conductive circuit is provided, and the other peelable sheet is peeled off, and the exposed curable adhesive layer (II) is placed on one side. Contacting one of the two sides of the printed wiring board (2) having a conductive circuit on both sides and adhering, and/or heating after contact, or peeling off and peeling off the adhesive sheet of claim 7 a sheet, the exposed curable adhesive layer (II) is in surface contact with one of the two-sided printed wiring board (2) having conductive circuits on both sides, and secondly peeling off another peelable sheet to expose the cured adhesive layer (II) Heating is performed while contacting the surface of the single-sided printed wiring board (1) having only one surface and having a conductive circuit, and the surface of the conductive circuit is not adhered, and/or adhered to the contact. A method for manufacturing a printed wiring board formed by laminating a plurality of conductive circuit layers, characterized in that a peeling sheet is peeled off from an adhesive sheet of claim 7 and an exposed curable adhesive layer is exposed (II ), one of the first two-sided printed wiring boards (2) having conductive circuits on both sides The surface contact is followed by peeling off another peelable sheet, and the exposed hardenable adhesive layer (II) is contacted with one surface of the second two-sided printed wiring board (2) having conductive circuits on both sides and adhered thereto, and/or After the contact sticks, it is heated. A method for manufacturing a printed wiring board formed by laminating a plurality of conductive circuit layers, characterized in that a peeling sheet is peeled off from an adhesive sheet of claim 7 and an exposed curable adhesive layer is exposed (II And contacting the surface of the first single-sided printed wiring board (1) having only one conductive circuit on the surface where the conductive circuit is not provided, and secondly peeling off another peelable sheet to expose the cured adhesive layer (II), The surface of the second single-sided printed wiring board (1) having the conductive circuit is contacted with the surface of the second single-sided printed wiring board (1), which is not provided with the conductive circuit, and is adhered, and/or adhered to the adhesive, and then heated. A method for manufacturing a printed wiring board formed by laminating a plurality of conductive circuit layers, characterized in that the adhesive composition (I) of claim 1 is applied to a surface having only a conductive circuit The surface of the first single-sided printed wiring board (1) on the side of the conductive circuit forms a curable adhesive layer (II), and secondly, the curable adhesive layer (II) has a conductive circuit while contacting only one surface. a surface of the second single-sided printed wiring board (1) on the side of the conductive circuit or a surface of the second single-sided printed wiring board (1) on which the conductive circuit is not provided and adhered, and/or adhered to the contact After that, heat is performed. Flexible printed cloth formed by laminating a plurality of conductive circuit layers A method of manufacturing a wire board, characterized in that the adhesive composition (I) of the first application of the patent application is applied to a conductive circuit side of a single-sided printed wiring board (1) having only one surface having a conductive circuit The surface forms a hardenable adhesive layer (II), and secondly, the hardened adhesive layer (II) is contacted with one surface of one of the printed wiring boards (2) having conductive circuits on both sides and adhered thereto, and/or Or heating after contact bonding; or applying the adhesive composition (I) of claim 1 to the surface of one of the two printed wiring boards (2) having conductive circuits on both sides, forming The curable adhesive layer (II), and secondly, the curable adhesive layer (II) is contacted with the surface of the conductive circuit side of the single-sided printed wiring board (1) having a conductive circuit on one surface and adhered thereto. And/or heating after contact sticking. A method for manufacturing a printed wiring board formed by laminating a plurality of conductive circuit layers, characterized in that the adhesive composition (I) of claim 1 is applied to both sides of a conductive circuit having two sides printed thereon a surface of one of the wiring boards (2) to form a hardenable adhesive layer (II), and secondly, a single-sided printed wiring board having a conductive circuit on one surface of the curable adhesive layer (II) (1) The surface of the conductive circuit is not provided and adhered, and/or heated after being adhered to the contact. A method for manufacturing a printed wiring board formed by laminating a plurality of conductive circuit layers, characterized in that the adhesive group of claim 1 is The object (I) is applied to one surface of the first two-sided printed wiring board (2) having a conductive circuit on both sides to form a hardenable adhesive layer (II), and secondly, the hardenable adhesive layer (II) Heating is performed while contacting one of the surfaces of the second two-sided printed wiring board (2) having the conductive circuits on both sides and being adhered and/or adhered to the contacts. A method for manufacturing a printed wiring board formed by laminating a plurality of conductive circuit layers, characterized in that the adhesive composition (I) of claim 1 is applied to a surface having only a conductive circuit The surface of the first single-sided printed wiring board (1) is not provided with a conductive circuit to form a curable adhesive layer (II), and secondly, the curable adhesive layer (II) is electrically conductive while contacting only one surface. a surface of the second single-sided printed wiring board (1) on the side of the conductive circuit or a surface of the second single-sided printed wiring board (1) on which the conductive circuit is not provided and adhered, and/or adhered to the contact After that, heat is performed. A method for producing a flexible printed wiring board formed by laminating a plurality of conductive circuit layers, characterized in that the adhesive composition (I) of claim 1 is coated to have conductivity on only one surface The surface of the single-sided printed wiring board (1) of the circuit is not provided with a surface of the conductive circuit to form a curable adhesive layer (II), and secondly, the curable adhesive layer (II) has a conductive circuit on both sides of the contact. The two sides of the printed wiring board (2) are printed on one surface and adhered, and/or heated after being adhered to the contact. A method for manufacturing a printed wiring board formed by laminating a plurality of conductive circuit layers, characterized in that the curable adhesive layer (II) of the adhesive sheet of claim 6 is electrically conductive with only one surface The surface of the first single-sided printed wiring board (1) of the circuit is in contact with the surface of the conductive circuit, and then the peelable sheet is peeled off, and the exposed curable adhesive layer (II) has a conductive circuit while contacting only one surface. a surface of the second single-sided printed wiring board (1) on the side of the conductive circuit or a surface of the second single-sided printed wiring board (1) on which the conductive circuit is not provided and adhered, and/or after contact bonding And heating is performed while; or, the hardened adhesive layer (II) of the adhesive sheet of claim 6 and the first single-sided printed wiring board (1) having a conductive circuit on only one surface are not provided The surface of the conductive circuit is in contact with each other, and then the peelable sheet is peeled off, and the exposed curable adhesive layer (II) is contacted with the conductive circuit of the second single-sided printed wiring board (1) having a conductive circuit on only one surface. Side surface and stick, and / Sticky paste after the contact, while heating. A method for manufacturing a printed wiring board formed by laminating a plurality of conductive circuit layers, characterized in that the curable adhesive layer (II) of the adhesive sheet of claim 6 is electrically conductive with only one surface The surface of the single-sided printed wiring board (1) of the circuit is in contact with the surface on the side of the conductive circuit, and then the peelable sheet is peeled off, and the exposed hardened adhesive layer (II) is electrically conductive on both sides of the contact. The surface of one of the printed circuit boards (2) is printed and adhered to the surface of the wiring board (2), and/or is adhered to the adhesive layer, or the hardened adhesive layer of the adhesive sheet of claim 6 ( II) contacting the surface of one of the two printed wiring boards (2) having the conductive circuits on both sides, and then peeling off the peelable sheet, and having the conductive layer formed on the exposed hardened adhesive layer (II) while contacting only one surface The surface of the single-sided printed wiring board (1) on the side of the conductive circuit is adhered and/or heated after being adhered to the contact. A method for manufacturing a printed wiring board formed by laminating a plurality of conductive circuit layers, characterized in that the curable adhesive layer (II) of the adhesive sheet of claim 6 is electrically conductive with only one surface The single-sided printed wiring board (1) of the circuit is not provided with the surface contact of the conductive circuit, and the peelable sheet is peeled off, and the exposed curable adhesive layer (II) is printed on both sides with the conductive circuit on both sides. a surface of one of the wiring boards (2) and adhered thereto, and/or heated after being contact-adhered; or the hardenable adhesive layer (II) of the adhesive sheet of claim 6 and two sides One of the two-sided printed wiring board (2) having a conductive circuit is in surface contact, and then the peelable sheet is peeled off, and the exposed curable adhesive layer (II) is contacted with one surface printed wiring having a conductive circuit on only one surface. The board (1) is not provided with a conductive circuit The surface is tacky and/or heated after contact. A method for manufacturing a printed wiring board of a plurality of laminated conductive circuit layers, characterized in that the hardenable adhesive layer (II) of the adhesive sheet of claim 6 and the conductive circuit on both sides One of the two-sided printed wiring board (2) is in surface contact, and then the peelable sheet is peeled off, and the exposed hardened adhesive layer (II) is contacted with the second two-sided printed wiring board (2) having conductive circuits on both sides. One surface is adhered and/or heated after contact. A method for manufacturing a printed wiring board formed by laminating a plurality of conductive circuit layers, characterized in that the curable adhesive layer (II) of the adhesive sheet of claim 6 is electrically conductive with only one surface The surface of the first single-sided printed wiring board (1) of the circuit is not provided with the surface of the conductive circuit, and then the peelable sheet is peeled off, and the exposed curable adhesive layer (II) is electrically conductive while contacting only one surface. The second single-sided printed wiring board (1) of the circuit is not provided with the surface of the conductive circuit and is adhered, and/or heated after being adhered to the contact.